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Indazoles and Condensed Types

Indazole reacts with potassium cyanate and acetic acid in ether to give indazole-2-carboxamide (m.p. 132-133") in poor yield. Heated above i ts melting point, the amide isomerizes to indazole-l-carboxamide (m.p. 155').356 1-Carboxylic acid esters of indazole and some of i ts homologs have been prepared by reaction of the alcohol with indazole-1-carboxylic acid chloride, obtained from indazole and phos- gene.357,35* They can also be obtained from o-aminobenzaldoxime according to Equation 46.359

Other than those from indazole itself, the following esters of 2-carboxylic acids have been made: ethyl 7-nitro-5-methylindazole-2-carboxylate, 359 ethyl 7-amino- 5-methylindazole-2-carboxylate, methyl 3-phenylindazole-2-carboxylate,360 ethyl 3-phenylindazole-2- ~arboxyla te ,~60 and the methyl and ethyl es ters of 3-methylindazole- 2-carboxylic acid. 3 6 1

CH=NOCOOR A

NHCOOR I kOOR

(46)

Indazole-3-carboxylic acid crystallizes in needles from dilute alcohol and melts at 258-259" with decomposition. It can be prepared by treatment of isatin at a low temperature with nitrous acid, followed by reduction (Equation 47),362-364 The acid is also obtainable f rom its nitrile, prepared from o -aminobenzonitrile by diazotization, 365-367 and by direct carbonation of indazole.210 The acid is decarboxylated above its melting point to give inda~ole .36~ It can be esterified directly;

fl

the methyl and ethyl es ters melt at 168-169" and 136-137" respect- ively.362 The ethyl es ter appears to be dimeric in naphthalene solution (see Section II).368 The benzyl thiolester, obtained directly, mel ts at 165-166O.369 Indazole-3-carboxylic acid gives two substances with thionyl chloride, but neither of these appears to be a true acid chloride. The mixture, however, yields the amide3'0 and various substituted amides when treated with ammonia or the appropriate amine. 364, 3 6 9 - 3 7 l The dimethylamide has been used in the synthesis of the indazole analog of tryptophan.364 The hydrazide and some of its derivatives have been reported to have anorexigenic The bromination of indazole- 3-carboxylic acid yields the 5-bromo derivative (m.p. 305-306").373

341

Chapter 10

Indazole-3-carboxylic acid is difficult to alkylate, but the 1-methyl compound results when it is heated with sodium and methyl i0dide.~63 When indazole-3-carboxylic acid is heated with acetyl chloride or anhydride, a substance results which is believed to have a diketopiper- azine-like structure (46).374

Indazole-3-carbonitrile is prepared by dehydration of the amide.375 It nitrates in the 5 -pos i t i 0n~5~ and behaves normally in most of i ts reactions. It methylates readily,366 as do the es te rs of indazole-3- carboxylic acid, which have been methylated, 363 benzylated, 355 allyl- ated, 3'6 carbomethoxylated, 376 and acetylated. 373 The methyl ester has been reduced to 3-indazolylcarbinol with lithium aluminum hydride ,364

46

A number of other indazole-3-carboxylic acids have been reported. For the most part, they have been made by one of two processes: alkylation of preformed acids or esters, 3559363.377 o r by treatment with alkali of the esters of 2, 4-dinitrophenylglyoxylic acid phenylhydra- z ~ n e s . ~ ~ ~ - ? a ~ By this latter method, a number of 6-nitro-1-arylindazole-3-carboxylic acids have been prepared (Equation 48). These acids a re useful intermediates, since the amino compound, readily obtained by reduction, undergoes the usual diazotization and replacement reactions. For example, 1 -arylindazole-3-carboxylic acids can be obtained in this ~ a y . 3 ~ 9 It may be mentioned that these acids provide a source for 3-indazole ketones, since they can be converted into acid chlorides, which wil l undergo the Friedel-Crafts reaction.379 Other ketones have been obtained by the reaction of indazole-3-car- bonitriles with Grignard reagents.3759383

Ar

342


A few other indazole-3-carboxylic acids have been prepared by special methods. Thus, 5-methylindazole-3-carboxylic acid has been obtained from 5-methylisatin as in Equation 47.3C2 2-Methylindazole- 3-carboxylic acid has been made by heating 1 - (N-methylacetamido)-3- isatoxime with 50% sulfuric acid (Equation 49).384 2-Arylindazole-3- carboxylic acids have been obtained by hydrolyses of their nitr i les, obtained by reduction of 3-cyanoindazole- 1 -oxides,3 85,386 which are discussed in Section XIII. It has been reported that the reaction of diacetylyohimbine with nitric acid yields 6-nitroindazole - 3-carboxylic acid.377

Although there would not appear to be any especial difficulty involved in their preparation, no indazoles containing carboxyl groups in the carbocyclic ring a re known. 4-Cyanoindazole, however, has been obtained from the corresponding amine by way of the Sandmeyer reac- t i0n.38~ Hydrolysis should produce the acid, and it would be expected that other carboxylic acids could be produced in a similar way, since numerous aminoindazoles a re known.

47

Some side chain acids of indazole are known. Most of them have been prepared by alkylation using a-bromo esters or acids. The treatment of indazole with sodium and ethyl bromoacetate affords ethyl-2-indazole acetate. However, heated with the bromoester alone, indazole yields both the 1- and 2-substituted esters.388 Either procedure with ethyl a-bromopropionate affords both esters. In all of these cases the indazole es ters can be ~ a p o n i f i e d . ~ 8 8 p -(2-Indazolyl)propionic acid (47) results directly when indazole is heated with p -bromopropionic acid.388 p -(1 -Indazolyl)propionic acid (48) is obtained by the hydrolysis of i ts nitrile, produced by the addition of indazole to acrylonitrile.366 3 -C yanoindazole adds to ac rylonitrile similarly .366

o,̂ r N C H Z C H ~ C O ~ H

48

Indazole-3-acetic acid can be produced by the air oxidation of o - hydrazinocinnamic acid in the presence of alkali.389 The acid is readily esterified and the esters behave normally.390 It is easily nitro- sated and undergoes bromination in the 5-p0s i t ion .~g~ Chromic acid oxidizes the bromo acid to 5-bromoindazole-3-carboxylic acid where-

343

Chapter 10

C H ~ N C O C H ,

as indaeole-3-acetic acid is completely oxidized. The pyrolysis of the acid gives 3 -me thy l inda~o le .~ 89 1 -Ethylindazole-3-acetic acid has been prepared by a method analogous to that for indazole-3-acetic acid and i ts reactions a re similar.

y-(2-amino-4-nitrophenyl) butyric e s t e r (Equation 5 0 ) . 3 9 2

p -(6-Nitro-3-indazolyl)propionic acid is obtained by diazotization of

XI. AMINOINDAZOLES

No 1- or 2-aminoindazoles a r e known. A large number of those with amino groups in other positions have been reported, however. Since the methods of preparation and some of the reactions of the 3-aminoindazoles differ from those of the other aminoindazoles, they are considered first .

The preparation of 3-aminoindazoles can be accomplished by the diazotization of o-aminobenzonitriles followed by r e d ~ c t i o n . ~ ~ ~ , ~ 9 3 Presumably, the reaction proceeds by way of the o-hydrazino compound. The preferred reducing agent is stannous chloride with hydrochloric acid. Other reducing agents, such as iron and acetic acid, zinc and acetic acid, and Raney nickel do not produce ring c l 0 s u r e . 3 9 ~ A second route to the 3-aminoindazoles uses reduction of azo-3-indazoles which

344


are obtained by the coupling of indazoles having the 3-position open o r as by-products in the synthesis of indazoles from o-toluidines. Thus, if mesidine is diazotized and the diazonium solution warmed with alkali, there resul ts 5, 7-dimethylindazole and 2,4, 6-trimethylben- zeneazo-3-(5, 7-dimethylindazole) (Equation 51). Reduction of the l a t t e r affords 3 -amino- 5 ,7 -dimethylindazole.

Although the 3-aminoindazoles have chemical properties much like those of the aromatic amines generally, they differ in some respects . Diazotization yields chiefly a diazohydroxide (49),394)395 which is much more stable than most compounds of the type. They r eac t with acids to give "indazoletriazolenes" (Bamberger). These compounds have been formulated by Bamberger as containing a four-membered ring (501,396-398 but according to Hantzsch, they a r e diazo compounds (51).399 At any rate, they undergo the usual substitution and coupling reactions of diazonium solutions. Another unusual reaction of 3- aminoindazoles is their oxidation with strong oxidizing agents such as chromic acid, permanganate, hydrogen peroxide or persulfates. The products a r e benzotriazines such a s 52.3947396)397,400 Weaker oxidizing agents, such as ferricyanide or air, a r e not effective.

H 49

+ -

50 51

3-Aminoindazole crystal l izes as white needles or leaves which melt a t 154" and a r e somewhat soluble in ~ a t e r . ~ 9 6 It can be p repa red by either general method discussed previo~sly.39~,393,396 It is basic (PK, = 3. 15)401 and readily fo rms sal ts with sulfuric, hydrochloric, oxalic, o r picric a ~ i d s . ~ 9 6 Silver nitrate or mercuric chloride f o r m "double salts ." Strong oxidizing agents produce the benzotriazine (52), but if air is bubbled through an alkaline solution, azo-3-indazole (53) results.402 The azo compound (m.p. 230") has weak acidic and basic properties. When treated with boiling aniline, it produces 3-aminoindazole and benzeneazo- 3 - indazole.

3-Aminoindazole undergoes acetylation with acetic anhydride and benzoylation with benzoyl chloride and sodium hydroxide. In both cases , diacylated products result.396 The diazotization of 3-aminoindazole produces an insoluble diazo hydroxide which melts at 128" with decomposition. Solution of the diazo hydroxide in acid and treatment with

345

Chapter 10

TABLE 7. Aminoindazoles by Reduction of Nitro Compounds

Indaz o le M.p. Reducing agent Yield Ref.

4 -amino - 151

4-amino- 5-methyl- 196

4-amino-6-methyl- 126

4 -amino- 7-methyl- 124

4-amino-7-acetamino- 160

4 -amino - 7 - acetamino - 5 -SO, H-

5-amino- 172

5 - amino - 4 - c hlor o - * 5-amino- 6-chloro-

5 -amino - 1 -methyl-

5-amino-2-methyl-

5-amino- 3-methyl-

5 -ammo - 4 -methyl-

5 - amino - 6 -methyl-

5-amino-6-methoxy-

5-amino- 1,3-diphenyl-

5-amino- 6-sulfonic acid

5-amino- 7-sulfonic acid

6- amino-

6-amino- 3-chloro-

6-amino- 5-chloro-

6-amino- 7-chloro-

6 -amino - 1 -methyl-

6-amino-2 -methyl-

181

183

149

178

127

105

233

197

224

165

2 10

210

206

209

203

184

193

184

173

130

169

FeSO, -NH, 409

H,(Ni) 92 293

FeSO, - NH , 440

H, (Nil 79 293

H,(Ni) 87 293

F e - HOAc 411

Fe-HOAc 411

FeSO, -NH, 7 5 412

H, (Nil 42 413,414

Zn-HC1 405

H, (Ni) 82 293

Sn-HC1 405

Fe-H,O 88 293

FeSO,-NH, 405

FeS0,-NH, 405

156

F e - HOAc 415

Fe-HOAc 415

Fe-H,O 90 293

SnC12-HC1 405

Fe-HOAc 411

Fe-HC1 411

H, (Ni) 81 401,414

Na, S 71 416

(NH,),S 417

(NH,),S; Sn-HC1 401

Fe-H,O 86 293

SnC 1, -HC 1 83 418

H, (Ni) 76 293

H,(Ni) 88 293

293

Na, S 40 293,416

H, (Ni) 7 5 293

Na, S 43 416

346


TABLE 7 (cont.)

Indazole ~ ~~

M.p. Reducing agent Yield Ref.

165

157

6-amino- 3 -methyl 205

212

6-amino- 5-methyl- 242

165

6 -amino- 7 -methyl- 182

6-amino- l-phenyl- 150

6-amino-3-phenyl-

6-amino- 1, 3-diphenyl-

6-amino-7-p-tolyl- 200

6-amino-7-phenyl-4-acetyl- 228

6- amino- 1 -phenyl- 4 - carbomethoxy 11 5

6 -amino- 7 - sulf onic acid

7-amino - 156

7-amino- l-methyl- 135

7-amino-2-methyl- 73

7-amino- 3 -methyl- 203

7-amino- 5-methyl-

'I-amino- 5-chloro-

7-amino-4-chloro-5-methyl**

7-amino- 6 - methoxy-

7-amino-5-methyl- l-carbethoxy-

7- amino- 5 -methyl- 4 - benzamido - 7- amino -4 - sulfonic acid

5, 6-diamino-

172(d.) (NH,),S

166 (NH,),S

163 Fe-HC1

195 Sn-HC1

215(d.)

A1-Hg

209

280 SnC1,

60 419

81 293

409

91 293

156

71 420

71 293

a4 293

42 1

422

422

423

423

423

41 1

424

72 293

90 293

156

406

42 5

410

406

410

425

410

411

85 293

* Resul ts when 5-nitroindazole is reduced with tin and hydrochloric acid. Apparently an aniline rearrangement takes place a s well as reduction.

acid. An aniline rearrangement probably occurs here also. ** Results when 7-nitro-5-methylindazole is reduced with tin and hydrochloric

347

Chapter 10

alkali affords "indazoletriazolene," which melts a t 106". "Indazoletria- zolene" fo rms sal ts with chloroplatinic acid and with si lver nitrate and mercuric chloride. It couples with phenols, and if boiled with alcohol furnishes indazole. 3-Chloroindazole resul ts if an "indazoletriazolene" solution is heated with hydrochloric acid, and 3-iodoindazole when potassium iodide is used,394,396, 398 Replacement by a cyano group has not been successful.394

?

52

53

3-Aminoindazole has been tested as an antimalarial, but has shown little promise.403 The p-aminobenzenesulfonyl derivative has been evaluated for its bactericidal value (see below).

Other 3-aminoindazoles whose properties appear to be s imilar to those of the parent compound a r e 5-methyl-3-aminoindazole (m.p. 190-191")394,398,402 and 5,7-dimethyl-3-aminoindazole (m.p. 133-134"),395,398,402 and 3-amin0-5-nitroindazole.~~~

Aminoindazoles having the functional group in the carbocyclic ring can usually be obtained by the reduction of the corresponding nitro compounds, which are readily available. A variety of reducing agents have been used (Table 7) and there appear to be no complications, except with tin and hydrochloric acid where an aniline rearrangement may occur,405,406 as shown in Equation 52.405 Other aminoindazoles can of course be obtained by substitution reactions with the aminoindazoles .

- Sn-HC1

O Z N W H H 2 N h H N (52)

The reactions of the 4-, 5 - , 6-, and 7-aminoindazoles are those of aromatic amines generally. They are rather weak bases (PKa for 6- aminoindazole = 3. 66)401 and although only slightly soluble in water, they are readily soluble in aqueous acids and may be reprecipitated f r o m such solutions by alkali, When 6-aminoindazole is treated with

348


chlorine, there results a "ketochloride, I t whose structure is believed to be that represented by formula 54,407 the evidence being its reduction to 4, 5, 7-trichloro-6-hydroxyindazole (55). If 6-aminoindazole is acetylated and then chlorinated, the normal reaction takes place, and 6-acetamino-7-chloroindazole is formed.408

55

The nitration of carbocyclic aminoindazoles leads to oxidation products, but 7-benzamidoindazole can be nitrated in the 4 - p o ~ i t i o n . ~ l o The sulfonation of the carbocyclic aminoindazoles requires vigorous conditions, but can be accomplished in good yield. Thus 5-aminoindazole affords 5-aminoindazole-4-sulfonic acid with 100% sulfuric acid at 120"; 6-aminoindazole yields 6-aminoindazole-7-sulfonic acid with fuming sulfuric acid at 120" and 6-aminoindazole-5,7-disulfonic acid at 165". '7-Aminoindazole gives 7-aminoindazole-4-sulfonic acid in 95% yield with 100% sulfuric acid, and 7-amino-4,6-indazoledisulfonic acid in 89% yield with 65% 0 1 e u m . ~ ~ Interestingly, 7-nitroindazole yields a mixture of the same two sulfonic acids when it is treated with sodium bisulfite (Equation 53).411

The aminoindazoles undergo acetylation readily to yield solids which can serve as deri~atives.4~1,4~5,4~6~4~5,4~6 The primary group reac ts readily, sometimes merely when the amine is heated with acetic acid. A second acetylation can occur which involves the imino hydrogen of the pyrazole ring, but it requires more vigorous conditions. Benzoyla- tion also occurs readily under Schotten-Baummn conditions,406,410,425 and either a mono- o r dibenzoylated product can result. The following other amino derivatives have been made: chloroacetyl,425 carbamyl (with ~ r e a ) , ~ ~ ~ s a l i c y l , ~ ~ 7 , 428 and benzoylacetyl428 (patented as couplers in color-forming emulsions).

p-Aminobenzenesulfonamidoindazoles have been prepared by the reaction of p-acetamidobenzenesulfonyl chloride with the appropriate aminoindazole and hydrolysis of the prod~ct.4~49429,432 In nutrient media, these "sulfa drugs" appear to have about the same antibacterial activity

349

Chapter 10

as sulfathiazole o r sulfadiazine.433 In addition to 3-aminoindazole, 5- (p-aminobenzenesulfonamido)-indazole and 2-methyl-7- @ -diethyla- minoethy1amino)indazole have been tested as antimalarials, but none has shown p r0mise .40~ The arylation of 6-aminoindazole has been effected with 2, 4-dinitrochlorobenzene434 and with 2, 3-dihydroxy- naphthalene. 435

Other reactions which have been reported t o take place with some, at least, of the aminoindazoles are the conversion to hydroxyindazoles by heating with aqueous sulfuric a ~ i d , 4 ~ 9 the formation of Schiff b a ~ e s , 4 ~ 6 , 4 1 9 ~ 4 ~ 5 the replacement of the amino group by a thiocyano group with thiocyanogen, and the Skraup reaction,408 by means of which pyridoindazoles are obtained (Equation 54).

The diazotization of carbocyclic aminoindazoles proceeds normally, and the solutions behave pretty much as expected. Replacement by hydrogen can be accomplished by use of hypophosphorous acid,413,423>424 e t h a n 0 1 , 4 ~ 6 > ~ 1 0 < 4 1 ~ or stannous sal ts . 409 Conversion to the phenol can be effected by heating the ~ o l u t i o n , ~ ~ 5 , ~ 1 6 > 4 1 7 > 4 2 6 or by the addition cf powdered g!ass,419,43e U I Lvric acid."S According to Fries and Tampke, 3 4 0 when 5-aminoindazole is diazotized and the solution heated, there results an azo compound (56) which is apparently produced by coupling of the newly formed phenol and unreacted diazonium compound.

56

The replacement of diazonium groups by halogen, 4 1 2 , 4 1 3 cyano, 409 and arsonic acid has been accomplished in the indazole series. The arsonic acids a re convertible &to arseno compound (Equa- tion 55). 437

Diazonium solutions from carbocyclic aminoindazoles couple with phenols t o give azo dyes.410,416,420)43*>43g,440 There is no information as to whether any a re used commercially. The aminoindazoles themselves react with diazonium solutions. If the reaction takes place in acid solution, an azo compound r e ~ ~ l t ~ ; ~ ~ ~ ~ ~ ~ ~ ~ 4 4 ~ in alkaline solu-

350


(55) A s = A s

H ‘N

H H 2 0 3 A s

H

tion, an azoamino compound is produced (Equation 56) .4l9 A number of indazole dyes a r e metalizable and have been ~ a t e n t e d . 4 4 ~ - 4 4 8 Certain indazole dyes seem to be especially suited for acrylic fibers.449-453

A T N=NNH a H2Nw (56)

H H N = N A r

W. INDAZOLESULFONIC ACIDS

Because of their considerable solubility in water and lack of sha rp melting points, the indazolesulfonic acids a re difficult to character ize and there are contradictory reports in the literature. Indazole-4-sulfonic acid has been prepared by the sulfonation of 7-aminoindazole and removal of the amino group via the diazonium salt.454 With phosphorus pentachloride it produces the sulfonyl chloride, m.p. 119-120”.

Indazole- 5-sulfonic acid has been obtained indirectly by the synthesis shown in Equation 57.454

NHCOCH3 NHCOCH, NHCOCH, H

NH2

351

Chapter 10

Indazole-6-sulfonic acid has been prepared f rom 5,6-dinitroindazole as shown by Equation 58. The disulfide 57 upon treatment with chlorine yields a mixture of 5-nitroindazole-6-sulfonyl chloride and 3-chloro- 5-nitroindazole - 6 - sulfonyl chloride, According to Petitcolas and Sureau,454 the sulfonation of indazole yields the 7-sulfonic acid, but von Auwers and Kleiner incline toward the 5-sulfonic acid structure.455 All of the indazolesulfonic acids so far discussed yield the co r re s - ponding hydroxy compound when heated with sodium o r potassium hydroxide, 4549 455

The diazotization of o -aminobenzophenone followed by treatment with sodium sulfite yields chiefly 3-phenyl-2-hydroxyindazole, but there is a i so produced a small amount of sodium 3-phenylindazole -2-sulfonate.456 Acidification of an aqueous solution of this substance yields a "sulfonoxide" written by von Auwers as 58 but probably better r ep re - sented by the inner salt formula 59. The same compound resul ts if 3-phenylindazole is treated with ethyl chlorosulfonate. 456 An analogous substance has been obtained from 3-methylindazole-2-sulfonic acid.

Among the other indazolesulfonic acids that have been described a r e two 2-phenyl- ? -indazolesulfonic acids,457 various nitroindazolesul- fonic acids,454)458 some hydroxy sulfonic a ~ i d ~ , ~ 6 ~ ~ ~ ~ ~ j ~ ~ ~ , ~ 5 ~ j ~ 6 ~ and a number of aminoindazolesulfonic acids.160j293, 454)460 ,461

58 59

Xm. INDAZOLES OF BIOCHEMICAL INTEREST

The indazoles may be regarded as a z a analogs of the indoles. A num- b e r of such analogs of compounds of biochemical interest have been

352


synthesized ostensibly for their possible antimetabolite propert ies . These include the indazole analogs of tryptophan,304 6-methyltrypto- phan,462 tryptamine,463 and serotonin.462-463 It appears that the indazole analog of tryptophan (tryptazan) interferes with the proper growth of certain yeasts4e6-4G9 and certain mutants of E. coli. 4 7 0 9 411 Effects on other organisms have also been d e s ~ r i b e d . 4 7 ~ - 4 7 5 Indazyl- acetic acid has growth-regulating properties like i ts indole a n a l 0 g . 4 ~ ~

XIV. INDAZOLE-1-OXIDES

A few indazole-1-oxides a r e known. The proof of structure depends upon the mode of synthesis and the fact that they may be reducedreadily to known indazoles. A number of closely allied methods have been used to prepare these compounds. o -Nitromandelonitrile, treated with an aromatic amine and a t race of sodium acetate produces 2-aryl-3-cyanoindazole-1-oxides (Equation 59).477 The same compounds can be ob-

C N

tained from o -nitrobenzaldehyde, the amine hydrochloride and potassium cyanide,477 or by way of the anil as shown in Equation 60.478 Alter- nately, the Schiff base in alcohol solution can be treated with potassium cyanide and acetic acid.480 According to Tanasescu and Tanasescu, the

reaction of ethyl o -nitro-phenylacetate with p - nitrosodimethylaniline in the presence of sodium carbonate or sodium phosphate yields ethyl 2-(p-dimethylaminophenyl)indazole-l-oxide-3-carboxylate. If the reaction proceeds as given by Equation 61, the nitroso compound must serve also as a reducing agent.48l

353

Chapter 10

3-Hydroxy-2-arylindazole oxides can be obtained from Schiff bases (Equation 62).482-484 The hydroxyl group r eac t s to form silver sal ts , which a r e readily convertible into ethyl e the r s by heating with ethyl iodide.

(62)

& H=NCeH5 N a 2 C 0 3 & r C s H 5

O2N

1 O2N NO2

0

Some of the indazole oxides have been reduced to indazoles by means of phosphorus trichloride,478 iron and hydrochloric acid,478 zinc and acetic acid477 or zinc and ethan01.48~ Chromic acid oxidation converts 3 -cyano-2-phenylindazole oxide into an azoxybenzenecarboxylic acid.478 This oxidation has been employed to establish the s t ructures of certain

d , 0 2 0 H "C,H,

1 0

60

azoxy c0mpounds.~79 The same cyano compound yields a sulfuric acid (60)) which reduction with iron and hydrochloric acid converts to o- aminobenzaniline (Equation 63).478 Hydrolysis of the sulfuric acid with hydrochloric acid furnishes a compound believed to be 2-phenylindazole- 1-oxide, which can also be reduced to o - a m i n o b e n ~ a n i l i d e . ~ ~ ~

354


L 0

XV. 3H-INDAZOLES (RING INDEX 1211)

3-H-Indazole (indiazole; indiazene; 61) is unknown, but a number of derivatives have been prepared. Certain substances obtainable by treatment of o-aminobenzaldoxime with nitrous acid have been described as indiazone oximes (62). The following examples have been

61 62

reported: indiazone oxime (m.p. 160-160. 5°),485 5,7-dimethylindiazone oxime (m.p. 180"),486 4, 7-dichloroindiazone oxime (m.p. 166"),486 4, 7(? ) -dibromoindiazone oxime (76"), 486 and 6 -hydroxy - 7- methoxy- indiazone oxime.487 These substances a re yellow, and upon t reatment with alkalies they yield o-a~idobenzaldehydes.~85 Treatment with acid produces a mixture of o -aminobenzaldehyde and o -hydroxybenzalde- h ~ d e . 4 ~ 6 Meisenheimer488 has pointed out that certain benzotriazine oxides (62a) have properties closely analogous to those of the indiazone oximes. The benzotriazine formula also explains more readily the easy conversion of these compounds to o -azidobenzaldehydes.

62a

If indazole is heated with benzaldehyde and zinc chloride a t loo", a solid (m.p. 140-141"), believed to be benzalindiazole (63) results.489 A number of spiro compounds, such as 64, which a r e formally indiazole derivatives a r e not considered in this section.

355

Chapter 10

HC6H5 05 63

& N

64

The coupling reaction between indazole and diazonium solutions leads to products which may be indiazole d e r i v a t i v e ~ , ~ ~ ~ - 4 9 ~ but there is insufficient information to distinguish among the three possible for - mulas 65,66, and 67.

H 65 66 67

XVL INDAZOLONES

Indazolone itself can be represented by Formula 68, but many compounds referred tn as indazolones how phenolic properties. Such CCE-

68 69 70

pounds a re probably best considered tautomers involving two o r more s t ructures such as 68,69 and 70.4939 4 g 4 The phenol formula 69 may predominate.495 Ionic s t ructures probably contribute.496 In some instances, existence of two compounds of presumably the same s t ruc- t u re has led to the suggestion that they a r e the indazolone and a hydroxyindazole. Similar considerations hold for 3-aminoindazoles which may be regarded a s iminoindazoles (71). Although they are listed as such in Beilstein, their reactions resemble more closely those of aromatic amines, and they have been t reated as such (Section XI). Some few known indazolones possess two substituents in the pyrazole ring (72) so that tautomerism is unlikely.

71 356 72


The f i r s t preparation of indazolone was by Emil Fischer who obtained it by heating o-hydrazinobenzoic acid (Equation 64).497 It was la te r

NHNH2 (64) H

found that for the preparation of indazolones generally, the s a m e end could be accomplished by heating the dry hydrochloride with phosphorus oxychloride498 o r merely by boiling an acid solution of the hydrazine.499-502 Sometimes the indazolone is formed spontaneously. 5009 503 Thus, heating 2-chloro-3, 5-dinitrobenzoic acid with hydrazine hydrate gives 5, 7-dinitroindazolone (Equation 65).504 o-Hydrazino e s t e r s can

0 O Z N a : )

(65) H

c1 I H

NO2

be maae to close rings ~ i m i l a r l y . ~ ~ 5 - 5 0 8 In isolated instances, indazolones have been prepared by the pyrolysis of hydrazinium salicyl- ate, 509 heating salicylhydrazides, 5 0 9 9 510 heating anthranilic acid hydrazides,5O9, 510, 511 the diazotization of anthranilic acid hydrazides, 513 and the treatment of o-carboxyphenylhydrazones with concentrated sulfuric acid (Equation 66). 514

H

1-Substituted indazolones can be prepared by the decomposition- rearrangement of azides of carbamic acids.515, 5 1 6 For example, heating N-phenyl-N-ethylcarbamic acid azide in xylene for 6 hours a t the boiling point provides 1-ethylindazolone (Equation 67) in 68%

yield. 515 1-Substituted indazolones a r e also formed when unsymmet- rically substituted hydrazines a r e heated with urea (Equation 68).5l7 2-Arylindazolones have been prepared by the treatment of hydrazo-

357

Chapter 10

R

benzene-o -carboxylic acids with phosphorus oxychloride in pyridine5I8 o r acetic anhydrides' o r by treatment of azobenzene-o-carboxylic acids with phosphorus pentachloride, 520-523 o r by heating azobenzene- 2 -a ldehyde~ ,5~1 , 5247 S25 and f rom azobenzenes and carbon monoxide with a cobalt carbonyl ~ a t a l y s t . 5 2 6 - 5 ~ ~ The preparation of indazolones is summarized in Table 8. Section IX should also be consulted for the preparation of 3-hydroxyindazoles.

The indazolone a r e yellowish solids most of which melt with decomposition. They a r e amphoteric, being soluble in sodium carbonate and ammonia s o l u t i o n s . ~ O O ~ 523 The basic function is weaker,523 but some hydrochlorides are known, 5169 531 and well-defined picrates have been obtained. 5 0 2 7 517 They have been t i trated potentiometrically in alcohol with sodium procedures and the product appears to be the 0-methyl e t h e 1 - , 5 ~ ~ ) 533, 534 although in one instance the AT-methyl ether has been reported. 513 B e n z o y l a t i o n ~ ~ ~ ~ , 5137 533 and acetylations506, 5317 533 have been performed and both mono and disubstituted products result. Either phosphorus oxychloride502, 5 1 2 , 503 or phosphorus pentachlo- ride534 produces the 3-chloroindazole, but the latter reagent may also cause chlorination. 2-Arylindazolones are converted by strong oxidizing agents such as nitric acid, chromic acid, sodium hypochlor - i te o r potassium permanganate into azobenzene-o-carboxylic acids. 520-5239 533 A number of nitroindazolones have been reduced to the corresponding amines. 5009 506, S o 7

Indazolone crystallizes from alcohol as tablets o r needles which have no t rue melting point. The decomposition point has been reported at f rom 242" to 249". It can be prepared by most of the methods previously mentioned but best from o-hydrazinobenzoic a ~ i d . 5 0 ~ It is weakly amphoteric and is soluble in aqueous sodium hydroxide. 512 Indazolone undergoes nitrosation readily. 5 l 2 It r eac t s with Tollens' 1 - e a g e n t 4 ~ ~ but not with Fehling's solution.497, 4 9 8 It gives a deep-red solution which probably contains the azo compound with lead acetate.535 Acety- lation at room temperature affords the 2-acetyl derivative (m.p. 188")409 but a t a higher temperature, the 1, 2-diacetyl derivative (m.p. 112")396, 423 results. The Schotten-Baumann reaction affords the 0 -benzoate519 or a dibenzoyl derivative.499 The 1-carbomethoxy and 1-carbethoxy derivatives a r e obtained when indazolone is treated with the appropriate chlorofomate and pyridine.499 Indazolone and phosphorus oxychloride in the presence of pyridine afford 3-chloroindazole in a yield of 70%.501 Indazolone has been stated to have analgesic, sedative, and spasmolytic p r0pe r t i e s .5~6 Magenta color couplers obtained from indazolones have been described. 537-545

Some have been methylated by the usual

358

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BL

E 8

. In

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6

275-

276

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Chapter 10

XVII. REDUCED INDAZOLES

Numerous partially reduced indazoles are theoretically capable of existence. Little is known of them, however, except for tetrahydroindazole 73 and its derivatives. Indeed, the location of the double bond or bonds in some of the partially reduced indazoles can not be considered settled.

The 4, 5,6,7-tetrahydroindazoles (cyclotetramethylenepyrazoles; cyclohexenopyrazoles) a r e best prepared by the reaction of a 2-substituted cyclohexanone with a hydrazine. For example, 4, 5, 6, 7-tetrahydroindazole itself is obtained in a 95% or better yield by the reaction of 2-hydroxymethylenecyclohexanone with hydrazine hydrate.s46 Other tetrahydroindazoles substituted in the carbocyclic ring can be obtained with the appropriately substituted cyclohexanone derivative. It is probable that the intermediate is a hydrazone, which should lead to a 2-substituted derivative when a substituted phenylhydrazine is employed (Equation 69). However, the 1-derivatives appear in many cases to be the more stable, so that the products often constitute a mixture of the 1- and 2-derivatives, o r may consist entirely of the 1-substituted compound.547, 550 The enol acetate or benzoate may provide a more convenient start ing material than the free hydroxymethylene compound.

H

G O N N H R a I > R (69)

CHOH + H , N N H R ---+

Other methods of preparation for tetrahydroindazoles that have been employed less generally a r e the ring closure of o-chlorocyclohexanone phenylhydrazone,551 the reaction of 2-chlorocyclohexenal with hydrazine hydrate,sz2 the addition of diazomethane to cyclohexene, which gives tetrahydroindazole in very poor yield, 5S3 and the hydrogenation of indazoles with platinum in acetic acid.554

best obtained employing the directions of Ainsworth.546 It melts a t 84" and boils a t 151" (14 mm). It is easily soluble in the common or - ganic solvents and is steam-volatile with difficulty. It f o r m s a silver salt and a picrate which melts at 155-156". It undergoes the reactions described in the following paragraph.

Tetrahydroindazole was first prepared by Wallach555 but is probably

362


The 4, 5,6,7-tetrahydroindazoles are dehydrogenated by sulfur to yield indazoles.556 Migration of an alkyl group may occur. Catalytic dehydrogenation (palladium on charcoal) seems superior. 546, 547 Tetrahydroindazoles having imino hydrogen undergo alkylation readily. The preferred reagent is a halide with an alkoxide a s an acid acceptor, though the alkyl halide alone, with heating, has also proved success - f ~ 1 . 5 ~ 8 9 549 Usually both 1- and 2-alkylated products a r e obtained. They have been most commonly separated by fractional crystall ization of the picrates o r perchlorates. Most of the alkylated tetrahydroindazoles a r e liquids. Various of their physical properties have been re- corded.558 N-Alkylated tetrahydroindazoles undergo further reaction with alkyl halides to yield tetrahydroindazolium ~ a l t s . 5 ~ ~ ) 559 Pyroly- sis of the salts yields a mixture of N-alkyltetrahydroindazoles. 559 Acylation of tetrahydroindazoles occurs readily and produces both 1- and 2- substituted products.550, 560

Derivatives of tetrahydroindazole-3-carboxylic acids are easily made and are useful for synthetic purposes. The easiest entree to these compounds consists in the reaction of ethoxalylcyclohexanone with a hydrazine (Equation 70).549, 5509 557 The ester group can be reduced by lithium aluminum hydride to the carbinol, which is an intermediate in the synthesis of the indazole analog of t r ~ p t a m i n e . 5 5 ~ The acid itself can be obtained by careful hydrolysis of the ester, or by direct synthesis, It melts a t 106-10'7". It and i t s homologs readily undergo decarboxylation.549 The acids form mixed anhydrides on heating with acid chlorides. 5 6 l

(70) CzH5

COCOOCzH, + H2NNH2

N H

Little is known of other functional groups on the tetrahydroindazole nucleus. A few 3-amino compounds have been reported from react ions involving o-cyanocyclohexanones and semicarbazide or h y d r a ~ i n e . 5 6 ~ They fo rm azo compounds on mild oxidation but do not undergo the usual diazotization reaction.

The discovery that tetrahydroindazolones 74 have analgesic and antipyretic p r 0 p e r t i e s 5 6 ~ has spurred research with these compounds. They are usually prepared by the reaction of ethyl cyclohexanone-2-

363

Chapter 10

carboxylate with a substituted hydrazine and alkylation of the product.564-577 Though most investigators believe that the group present in the hydrazine finds itself in the 2-position in the product and that alkylation occurs in the 1-position, there is not complete agreement. Some of the indazolones yield molecular complexes with substituted barbituric a ~ i d s . 5 ~ ~ 3 579

Their spectral properties indicate that the indazolones a r e resonance hybrids to which ionic s t ructures are heavy contributors.580

Other than the tetrahydroindazoles mentioned above, few reduced indazoles having only one double bond have been reported and the information is fragmentary. A compound described as A l , 7a -hexa- hydroindazole has been obtained f rom 2-hydroxymethylcyclohexanone and h y d r a ~ i n e . 5 8 ~ The 3, 3,6-trimethvl derivative of this compound is

obtained from pulegone and hydrazine (Equation 71).5B2-584 Hexahy- droindazoles have been reported with the double bond in the 1, 2-position,s85 the 2,3-position,586 and the 3a, 7a-p0sit ion.58~

0 II

0 U CH,

f CH,N2 -> (72)

The reaction of certain catechol derivatives with diazohydrocarbons gives rise to partially reduced indazoles.588, 589 For example, 2-ace- toxy-2-methyl-3, 5-cyclohexadienone reacts with diazomethane as shown by equation 72.588 2-Hydroxy-2, 3, 5-trimethyl-3, 5-cyclohexadienone i s reported to react with diazomethane as given by Equation 73.589

give partially reduced indazoles.59°-5g3 For example, "C-acetyldi- methyldihydroresorcinol" reacts with phenylhydrazine as shown in equation 740590-591 The phenylhydrazone of the ketone may be the pro- d ~ c t . 5 ~ ~ 2-Acetyl-1, 3-cyclohexandione is reported to react as in Equation 75. 593 Similarly, 2-propionylcyclohexanone is described as

Similar compounds have been found to r eac t with phenylhydrazine to

364


reacting with semicarbaxide to give a compound having s t ructure 75 o r 76. S g 4 Likewise, the reaction of the diester 77 with phenylhydrazine leads to a compound of unknown structure which, on treatment with alkali, furnishes a product whose structure is that represented by 7 8 . 5 9 5

78 C6H5

79

1, 3-Cyclohexadiene r eac t s with the C-chloro derivative of benzaldehyde phenylhydrazone in the presence of triethylamine t o give the partially reduced indazole 79 in 75% yield.596 The compound affords a 79% yield of 1, 3-diphenylindazole on dehydrogenation with chlora- nil. 596

365

Chapter 10

REFERENCES

1.

2.

3.

4.

5.

6.

7.

8.

9.

10.

11.

12.

13.

14.

15.

16.

17.

18.

19.

20.

21.

22.

23.

24.

2 5.

26.

27.

28.

29.

30.

31.

32.

F ischer , E.,=., 13, 679 (1880).

F i sche r ,E . , and Kuze1,&,221,261 (1883).

Pa t te rson and Capell, The Ring Index, Ed. 2. The Amer ican Chemical Society, Washington 1980, p 159.

Fabel, Thes is , iiber d a s Indazol und uber s e in Ahnlichkeit mit d e m Naphthalin, Leipzig, 1930.

Paal and L u c k e r , B e r . , 2 7 , 4 7 (1894).

von Auwers and Duesberg,-, 53B, 1179 (1920).

von Auwers and Schaich,=, 54B, 1738 (1921).

von Auwers,Sitz.-Ber. Bef. ges . Naturwiss. M a r b u r g , l 9 2 5 , 1 8 p p . ; S , 2 1 , 3893 (1927); Chem. Zentr. , 1926, I, 2347.

von Auwers ,&,437,63 (1924).

von Auwers, Hugel, and Ungemach,&., 527,291 (1937).

F r i e s , Fabel, and Eckhard t ,&, 550 ,31 (1941).

Hayashi, Bull. Inst. Phys. Chem. Resea rch (Tokyo), 9 , 9 1 1 (1930); Abs t rac ts , 3, 88 (1930); C A , 2 5 , 1 8 2 4 (1931).

von Auwers and von Meyenburg ,= ,24 ,2370 (1891).

von Auwers and Sundheimer, %, 29,1255 (1896).

von Auwers and Huttenes, Ber . , 55B, 1112 (1922).

von Auwers and Schaum, Ber . , 62B, 1671 (1929)

Barc lay , Campbell, and Dodds, J. Chem. SOC., 1941,113.

Schuett and Zimmermann, B e r . Bunsenges. Physik. Chem., 67, 54 (1963); - C.A., 58,13301 (1963).

Polansky, Rieger , and Derf l inger , Monatsh. Chem., 92,1131 (1961).

Rousseau and Lindwall, J. Am. Chem. SOC., 72,3047 (1950).

Kohlrausch and Seka, Ber., 73B, 162 (1940).

Staab and Mannschreck, Te t rahedron Le t t e r s , 1962, 913.

von Auwers and Huttenes, Ber . , 55B, 1112 (1922).

Fabel, Thes is , h e r das Indazol und uber s e in Ahnlichkeit mit dem Naphthalin, Le ipzig , 1 9 3 0.

F r i e s , Fabe l , and Eckhardt,&., 550 ,31 (1941).

Polansky and Derflinger, Monatsh. Chem. ,92 ,1114 (1961).

Hayes and Hunter, J. Chem.Soc., 1941, 1.

Snyder, Thompson, and Hinman, J. Am. Chem. SOC., 74,2009 (1952).

Bamberger ,&,305,289 (1899).

N o e l t i n g , K , 37,2556 (1904).

Freundler , Bull. SOC. Chim., [4], 9 , 778 (1911).

Reich and Turkus, Bull. SOC. Chim., [4], 21, 107 (1917).

-

-

~

-

366


Homing, pr ivate communication.

Piozzi and Dubini, Gazz. Chim. Ital., 89,638 (1959).

P o r t e r and Pe te r son , Org. Syntheses, Col. Vol. 111,660 (1955).

Huisgen and Nakaten,&., 573,181 (1951).

Bamberger , Ann., __ 305 289 (1899).

Noelting,-, 37,2556 (1904).

33.

34 *

35.

36.

37.

38.

39.

40.

41.

42.

43.

44.

45.

46.

47.

48.

49.

49a.

50.

51.

52.

53.

54.

55.

56.

57.

58.

59.

63.

61.

62.

63.

64.

65.

66.

67.

Cook, Dickson, Jack, Loudon, McKeown, MacMillan, and Williamson,J. Chem. SOC., - 1950,139.

Bamberger and von Goldberger,&, 305,339 (1899).

Michel and G r a n d m o u g i n , w , 25,2349 (1892).

Witt, Nolting, and G r a n d m o u g i n , w , 23,3635 (1890).

F i e se r , J. Am. Chem. Soc.,48,1097 (1926).

von Auwers and Schwegler, Ber. , 53B, 1211 (1920).

Brand and Eisenmenger, J. Prakt . Chem., 87,498 (1913).

Bamberger and von Goldberger, &., 305,363 (1899).

Davies, J. Chem.Soc.,1955,2412.

Gabriel and Stelzner , B z , 2 9 , 3 0 3 (1896).

Sureau and Pe rno t , Bull. Soc. Chim. France,1958,152.

Sureau, Bull. SOC. Chim. F rance , 1956,622.

Dadswell and Kenner, J. Chem. SOC., 1927, 580.

--_

Qvist and Gardshol, Acta Acad. Aboensis, Math e t Phys. ,22, No. 33, 3 (1961); - C.A., 56,1444 (1962).

Pschor r and Hoppe,=,43,2543 (1910).

Rousseau and Lindwall, J. Am. Chem. SOC., 72,2047 (1950).

von Braun and Rawicz,=,49, 799,808 (1916).

De T a r and Yun-wen Chu, J. Am. Chem. SOC., 76,1686 (1954).

Eliasberg and Friedlgnder , =, 25,1752 (1892).

von Auwers and Stradter,&, 59B, 529 (1926).

von Auwers and Duesberg,=, 59B, 1179 (1920).

von Auwers ,=,29,1255 (1896).

Corbellini and Cecchi, Gazz. Chim. Ital., 63,489 (1933).

Dziew6nski and Sternbach, Bull. Intern. Acad. Polonaise, C las se Sci. Math. Nat., 1935A, 333; 2 , 3 0 , 2 9 7 2 (1936).

Re i s se r t and Gruber,-,42,3716 (1909).

Moore and Woitach, Bri t . Patent 816,382 (1959);%,, 55,188 (1961).

Cooper, J. Chem. Soc.,1958,4212.

Aron and Elvidge, Chem. Ind., 1958,1234.

Parnel l J. Chem. SOC., 1959,2363.

Zincke, - Ann., 339,202 (1905).

367

68.

69.

70.

71.

72.

73.

74.

75.

76.

77.

78.

79.

80.

81.

82.

83.

84.

85.

86.

87.

88.

89.

90.

91.

92.

93.

94.

95.

96.

97.

98.

99.

Chapter 10

Zincke and Malkomesius, &., 339,224 (1905).

Zincke and Kuchenbecker,&, 339,235 (1905).

Zincke and Ellenberger,&. ,339,209 (1905).

Beaver, De la Mare, Johnson, and Klassen, J. Chem. SOC., 196h 988.

Simonov, Martsokha, and Pozharski i , Zh. Obshch. Khim., 33,1001 (1963).

Schad,&,26,216 (1893).

Ainsworth, J. Am. Chem. SOC. ,80,967 (1958).

Fischer and K u z e l , 4 , 2 2 1 , 2 6 1 (1883).

Klieeisen, =,27,2549 (1894).

Jacobson and H u b e r , B 3 , 4 1 , 660 (1908).

Huisgen and Nakaten,&, 573,181 (1951).

Rondesvedt and Blanchard, J. Am. Chem. SOC., 77,1769 (1955).


Bri t , Patent 599,834,March 28,1948 to SOC. Anon. de Matieres Colorantes; - C . A . , 4 2 , 7538 (1948).

Suschitzky, J. Chem. Soc.,1955,4026.

Kovach and Barnes, J. Am. Chem. SOC., 76,1176 (1954).

CarrC, Ann. Chim., [8] ,6 ,408 (1905).

CarrC, Compt. Rend., 140, 664 (1905).

Freundler and de Laborderie , Bull. SOC. Chim., [4 ] , 1, 234 (1907).

Paal ,Ber . ,24,3058 - (1891).

Bamberger, x, 44,1966 (1911).

Freundler , Bull. SOC. Chim., [4] , 9,601 (1911).

Chardonnens and Heinrich, Helv. Chim. Acta, 23, 1399 (1940)

Chardonnens and Buchs, Helv. Chim. Acta,29,872 (1946).

Freundler , Compt. Rend,, 136, 1136 (1903).

Freundler, Bull. SOC. Chim., [3], 29, 742 (1903).

Freundler, Bull. SOC. Chim., [3],31,862 (1904).

Freundler , Bull. SOC. Chim., [3], 31,868 (1904).


Freundler , Compt. Rend., 137,521 (1903);138,1425 (1904).

Freundler,Bull .Soc. Chim., [3],31,38 (1904).


a

100. FriedlPnder and Lenk,=,45,2083 (1912).

101. CarrC,Bull .Soc. Chim., [4], 5,283, (1909).

102. Freundler, Compt. Rend., 143,909 (1906).

103. Freundler , Bull. SOC. Chim., [4], 1 ,228 (1907).

104. Freundler , Compt. Rend., l49,1135 (1909).

368

105.

106.

107.

108.

109.

110.

111.

112.

113.

114.

115.

116.

117.

118.

119.

120.

121.

122.

123.

124.

125.

126.

127.

128.

129.

130.

131.

132.

133.

134.

135.


Freundler,Bull .Soc. Chim.,[4],9,601 (1911).


Freundler, Compt. Rend., 137,983 (1903).

Heller,%,49,2757 (1916).

Carre,Ann. Chim., [ E l , 19,206 (1910).

Heusler, Ber., 24, 4156 (1891).

Paal,=,24,3058 (1891).

Paal and F r i t z w e i l e r , E , 25,3167 (1892).

Paal and F r i t z w e i l e r , E , 2 5 , 3 5 9 0 (1892).

Busch and Francis , J. Prakt. Chem., 51,272 (1895).

Busch and F ranc i s , J. Prakt . Chem., 52,377 (1895).

Busch and Volkening, J. Prakt. Chem., 52,380 (1895).

Busch and Hartman, J. Prakt. Chem., 52,404 (1895).

Busch and Heinen, J. Prakt. Chem., 52,389 (1895).

Busch and Hartman, J. Prakt. Chem., 52,398 (1895).

Reich and Ghazarian, Bull. SOC. Chim., [4], 19,259 (1916).

von Auwers and von Meyenburg,-,24,2370 (1891).

Bischler,=, 26, 1891 (1893).

von Auwers,=., 58B, 2081 (1925).

von Auwers and Frese,&.,450,273 (1927).

Bamberger and Demuth,%, 35,1885 (1902).

Bamberger,%, 55B, 3371 (1922).

Busch,=.,2'7,2897 (1894).

Krbechet and Takimoto, J. Org. Chem., 29,1150 (1964).

Cadogan and Searle , Chem. Ind. (London), 1963,1282.

Meisenheimer and Senn,%, 59B, 199 (1926).

Borsche and Scriba Ann., 540, 83 (1939).

Borsche and Herbert ,&, 546,293 (1941).

Hunziker, Lehner,Schindler, and Schmutz, Pharm.Acta Helv., 38,539 (1963).

Borsche and Wagner-Roemmich,&, 546,273 (1941).

Fuson and Hammann, J. Am. Chem. SOC., 74,1626 (1952).

-

-

136. Szmant and Harmuth, J. Am.'Chem.Soc., 81,962 (1959).

136a. Loudon and McCapra, J. Chem. SOC., 1959,1899.

137, Borsche and Diacont,&, 510,287 (1934).

138. Reid and Dietrich, Angew. Chem., 75,476 (1963);&, 666,135 (1963).

139. von Auwers and Frese,&, 58B, 1369 (1925).

140. Reich and Turkus, Bull. SOC. Chim. France, [4],21,107 (1917).

141. Reich and Gaigailian,=.,46,2380 (1913).

369

142.

143.

144.

145.

146.

147.

148.

149.

150.

151.

152.

153.

154.

155.

156.

157.

158.

159.

150.

161.

162.

163.

164.

165.

166.

167.

168.

169.

170.

171.

172.

173.

174.

175.

176.

177.

Chapter 10

Reich, Bull. SOC. Chim. France,[4] ,21,111 (1917).

Reich and Nicolaeva, Helv. Chim. Acta, 2, 84 (1919).

M e y e r , V . , B ~ . , 2 2 , 3 1 9 (1889).

Borsche and Butschli,&, 522,285 (1936).

Borsche,Ber. ,42,601 (1909).

von Auwers and Lange,-, 55B, 1139 (1922).

von Auwers and Demuth,&,451,282 (1927).

Fischer and Tafel ,&,227,303 (1885).

von Auwers and Lohr, J. Prakt. Chem., 108,297 (1924).

F r i e s and Roth,& 404, 81 (1914).

F r i e s and Weldert,&.,454,314 (1927).

F r i e s , Fabel, and Eckhardt,&, 550,31 (1941).

von Auwers and Kleiner, J. Prakt . C h e m . , l l 8 , 6 7 (1928).

Peti tcolas and Sureau, Bull. SOC. Chim. F rance , 1950,466; French Patent 1,005,327 (1952);*., 51,16561 (1957).

Sureau and Pernot, Bull. SOC. Chim. F rance , 1958,152.

Savitskaya, Tarasevich, and Shchukina, Zh. Obshch. Khim., 31,3255 (1961).

Paal and Li icker ,Ber . ,27,47 (1894).

Sureau and Mingasson, U.S. Patent 2,787,515, equivalent to Brit. Patent 775,829 (1957); C.A., 51,14279 (1957).

Dz+x,Eri! . Pa tmt 744,212 ( 1 9 5 6 ) ; ~ , 51,481 (1957).

von Auwers and Dusterdieck, J. Prakt . Chem., 118,53 (1928).

von Auwers, Sitz.-Ber.Ges. Bef.ges.Naturwiss.Marburg. 1925,137; C.A., 21,3982 (1927); Chem. Zentr., 1926, I, 2347

von Auwers and Allardt,=, 57B, 1098 (1924).

von Auwers and Lohr , J. Prakt .Chem., 108,297 (1924).

Pozharskii , Martsokha, and Siminov, Zh. Obshch. Khim., 33,1005 (1963).

Martsokha, Pozharskii , and Siminov, Zh. Obshch. Khim., 34,1317 (1964).

vonAuwers and DBesberg,%, 53B, 1179 (1920).

von Auwers and Schaich,=, 54B, 1738 (1921).

von Auwers and Pfuhl,=,58B, 1360 (1925).

von Auwers and Kleiner, J. Prakt . Chem., 118,67 (1928).

von Auwers and Allardt, Ber., 59B, 95 (1926).

von Auwers,Hiigel, and Ungemach,&, 527,291 (1937).

Barclay, Campbell, and Dodds, J. Chem. SOC., 1941,113.

von Auwers and S c h w e g l e r , E . , 53B, 1211 (1920).

von Auwers and Demuth,&,451,282 (1927).

Davies, J. Chem. SOC., 1955,2412.

Zhao and Shchukina, Zh. Obshch. Khim., 29,1012 (1959).

-

~

370


178.

179.

180.

von Auwers, Ber. , 52B, 1330 (1919).

von Auwers, Ernecke, and Wolter,&,478, 154 (1930).

von Auwers and Hiittenes,=, 55B, 1112 (1922).

-

181. von Auwers and Dereser ,&, 53B, 1211 (1920).

182. von Auwers and StrBdter,=, 59B, 529 (1926).

183. Rousseau and Lindwall, J. Am. Chem. SOC., 72,3047 (1950).

184. von Auwers and Diiesberg,=., 53B, 1179 (1920).

185. von Auwers and Kleiner, J. Prakt . Chem., 118,67 (1928).

186. von Auwers and Pfuhl, Ber. , 58B, 1360 (1925).

187. von Auwers and Schaich,=., 54B, 1738 (1921).

188. von Auwers, Diisterdieck, and Kleiner,=.,GlB, 100 (1928).

189. Paal,%, 24, 959 (1891).

190. von Auwers and Hiittenes,&, 55B, 1112 (1922).

191. von Auwers and Lohr, J. P rak t .Chem., 108, 297 (1924).

192. von Auwers and Diisterdieck, J. Prakt. Chem., 118,53 (1928).

193. von Auwers and Allardt, B?, 57B, 1089 (1924).

194. Bamberger,&, 305,308 (1899).

195. von Auwers,=, 52B, 1330 (1919).

196. von Auwers and DCesberg,=., 53B, 1179 (1920).

197. von Auwers and Schwegler,=, 53B, 1211 (1920).

198. von Auwers and Lange,=.,55B, 1139 (1922).

199. Meisenheimer and Diedrich, B x . , 57B, 1715 (1924).

200. von Auwers, Ber . , 57B, 1723 (1924).

201. von Auwers and Allardt,&.,438,1 (1924).

202. von Auwers, Ber. , 58B, 2081 (1925).

203. Meisenheimer and Senn, Be r . , 59B, 199 (1926).

204. von Auwers, Ernecke, and Wolter,&, 478,154 (1930).

205. von Auwers and Demuth,&, 451,282 (1927).

206. von Auwers and Strijdter, Ber. , 59B, 529 (1926)

207. Zhao and Shchukina, Zh. Obshch. Khim., 29,3720 (1959).

208. Ziegler and Wolf, Monatsh. Chem., 93,1441 (1962).

209. von Auwers and F r e s e , B x . , 59B, 539 (1926).

210. Henkel e t C ie G.M.b.H., Bri t . Patent 816,531 (1959);C.A., 54, 1552 (1960).

211. Birkofer, Richter, and Ritter, Chem. Ber., 93, 2804 (1960).

212. Sureau and Pernot , Compt. rend. congr. intern. chim. ind., 31e, Liege, 1958, 2, 469;=.,54, 22587 (1960)

213. Fischer and Kuzel,&, 221, 261 (1883).

214. Fischer and Tafel , Ann., 227, 303 (1885).

-

-

- -

-

--

- 371

Chapter 10

von Auwers and DGesberg,=,53B, 1179 (1920).


215.

216.

217.

218.

219.

220.

221.

222.

223.

224.

225.

226.

227.

228.

229.

230.

231.

232.

233.

234.

235.

236.

237.

238.

239.

240.

241.

242.

243.

244.

245.

246.

247.

248.

249.

Jensen and Friediger, Kgl. Danske Videnskab; Mat-fys.-Medd., 20, No. 2 0 , l (1943). -- C. A., 39, 2068 (1945); Chem. Zentr., 19441, 416.

Rousseau and Lindwall, J. Am. Chem. S O ~ . , 72,3047 (1950).

Thompson, Thesis, A Study of the Chemistry of Indazole, University of Illinois, 1949.

Kohlrausch and Seka, Ber., 71B, 1563 (1938); 73B, 162 (1940).

Stephenson, Org. Syntheses, Coll. Vol. III, 475 (1955).

Ainsworth, Org. Syntheses, Coll. Vol. IV, 536 (1963).

Huisgen and Bast, Org. Syntheses, 42,69 (1962).


Albert, Goldacre, and Phillips, J. Chem. SOC., 1948, 2240.

Jacobson and Huber, - Ber.,41,660 (1908).

Schad, - Ber., 26,216 (1893).

Fr ies , Fabel, and Eckhardt,&, 305, 339 (1899).


Fischer and Seuffert, Ber., 34, 795 (1901). - Cambi and Canonica, Atti Accad. Nazl. Lincei, Rend., Classe Sci. Fis., Mat. e Nat., 20,17 (1956).

Siminov. Martsokha. and Pozharskii, Zh. Obshch. Khim., 33,1001 (1963).

ibid., 32, 2388 (1962).

-

Martsokha, Materialy-4-oi [Chetvertoe] Nauchn. Konf. Aspiriantov Sb, 106.

von Auwers and Dtesberg,=, 53B, 1179 (1920).

von Auwers and Kohlhaas,&,437,36 (1924).

von Auwers and von Meyenburg,=., 24,2370 (1891).

von Auwers,=,52B, 1330 (1919).

Bamberger and von Goldberger, &, 305,363 (1899).

Gabriel and Stelzner, B s , 29,303 (1896).


Bamberger, - Ann., 305, 289 (1899).

Bamberger, - Ann., 305,308 (1899).

von Auwers and Kleiner, J. Prakt. Chem., 118,67 (1928).

Borsche and Diacont,Ann., - 510,287 (1934).

Borsche and Biitschli,&, 522, 285 (1936).

von Auwers and Frese, B s , 58B, 1369 (1925).

Reich and Gaigailian, BE., 46B, 2380 (1913).

Paal and Krecke,=, 23,2634 (1890).

1962,

372


Paal, - Ber., 27, 2897 (1894).

Paal and LGcker,=., 27,47 (1896).

Busch, - Ber., 27,2897 (1894).

Freundler, Bull. SOC. Chim. France, [3], 29,742 (1903).

Freundler, Bull. SOC. Chim. France, [3], 31,868 (1905).


Busch and Francis, J. Prakt. Chem., 51,272 (1895).

Paal and Fritzweiler, Ber., 25, 3167 (1895).

Busch and Francis, J. Prakt. Chem., 52,378 (1895).

Busch and Volkening, J. Prakt. Chem., 52,380 (1895).

Busch and Hartmann, J. Prakt. Chem., 52,404 (1895).

Paal and Fritzweiler,=, 25,3590 (1892).

Reich and Ghazarian, Bull. SOC. Chim., [4], 19, 259 (1916).

von Auwers and S t r a d t e r , E , 59B, 529 (1926).

von A u w e r s , g , 29,1255 (1896).

von Auwers and Huttenes,=., 55B, 1112 (1922).

Corbellini and Cecchi, Gazz. Chim. Ital., 63,489 (1933).

-

250.

251.

252.

253.

254.

255.

256.

257.

258.

259.

260.

261.

262.

263.

264.

265.

266.

267.

268.

269.

270.

271.

272.

273.

274.

275.

276.

277.

278.

279.

280.

281.

282.

283.

284.

285.

DziewBnski and Sternbach, Bull. Intern. Acad. Polonaise, Classe Sci. Math. Nat., 1935A, 333; C.A., - 30, 2972 (1936). - Borsche and Scriba, Ann., 540,83 (1939)

Schaum and Rorig, Z. Anorg. Chem., 132, 77 (1923).

von Auwers and Schaum, Ber., 62B, 1671 (1929).

Barben and Suschitzky, J. Chem. SOC., 1960,672.

von Auwers and Lange,%., 55B, 1139 (1922).

von Auwers, HGgel, and Ungemach,&, 527,291 (1937).


Fischer and Seuffert,=, 34,795 (1901).

Stephenson, Org. Syntheses, Coll. Vol. ID, 475 (1955).

Bamberger,=., 32,1773 (1899).


Kenner and Curtis, J. Chem. SOC., 105, 2717 (1914).

Fischer and Tafel,&, 227,303 (1885).

von Auwers and Demuth,&.,451, 282 (1927).

von Auwers and Schwegler, =, 53B, 1211 (1920).

von Auwers, Ernecke, and Wolter,*,478,154 (1930).

Bamberger, - Ann., 305, 289 (1899).

Fischer and Blochmann, Ber., 35,2315 (1902).

__

-

- 373

Chapter 10

Freundler, Bull. SOC. Chim., [4], 9 , 778 (1911).

Freundler,Compt.Rend., 152,1256 (1911).


Petitcolas and Sureau, Bull, SOC. Chim. France, 1950,466.

Freundler, Bull, SOC. Chim. France, [4], 9,735 (1911).

Pearman, J.Chem. SOC., 119,717 (1921).

Fr ies and Tampke,&,454,303 (1927).

Davies, J. Chem. SOC., 1955,2412.

N o e l t i n g , E , 37, 2556 (1904).

Zincke and Malkomesius,&, 339, 224 (1905).

Brand and Eisenmenger, J. Prakt. Chem., 87,487,498 (1913).

Borsche and Herbert,Ann., 451, 282 (1927).

von Auwers and Demuth,Ann.,451,282 (1927).


von Auwers and Frese,=, 58B, 1369 (1925).

von Auwers and S c h w e g l e r , E . , 53B, 1211 (1920).

von Auwers and Kleiner, J. Prakt. Chem., 118,67 (1928)

__

286.

287.

288.

289.

290.

291.

292.

293.

294.

295.

296.

297.

298.

299.

300.

301.

302.

303.

304.

305.

306.

307.

308.

309.

310.

311.

312.

313.

314.

315.

316.

317.

318.

319.

Stauffer, U.S. Patent 2 497 917 (1950) to Eastman Kodak Co.; - C.A., 44, 9841 (1950).

Hanson and Richey, U.S. Patent 2 496 940 (1950) to Eastman Kodak Co.; C.A.,44,5747 (1950).

Passal, U.S. Patent 2,684,327 (1954);=, 48,10462 (1954).

Witt, Nolting, and G r a n d m o u g i n , s , 23,3635 (1890).

Fieser, J. Am. Chem. S O C . , ~ ~ , 1097 (1926).

Fr ies , Fabel, and Eckhardt, &, 550,31 (1941).

Petitcolas and Sureau, Bull. SOC. Chim. France, 1950,466.

Hahn and Just, Ber., 65B, 717 (1932).

-

- Flett, U.S. Patent 2 469 378 (1949) to Allied Chemical and Dye Gorp.;%, 43,6846 (1949).

Reich and G a i g a i l i a n , g , 46, 2380 (1913).

Sureau, Bull. SOC. Chim. France, 1956,622.

Kenner and Witham, J. Chem. SOC., 119,1053 (1921).

Vesely and Medvedeva Collection Czechoslav. Chem. Commun., 9, 176 (1937); C. - A,, 31, 5355 (1937).

Borche and Diacont,Ann., - 510,287 (1934).

Borsche and Scriba,+, 540,83 (1939).

von Auwers and Frese, BE, 59B, 539 (1926).

Gabriel and Stelzner,%, 29,303 (1896).

374


320. Bamberger and Demuth,=, 35,1891 (1902).

321. Bamberger, Ber. , 55B, 3371 (1922).

322. von Auwers, Ber. , 29,1255 (1896).

323. von Auwers and Hiittenes,=., 55B, 1112 (1922).

324. von Auwers and Strijdter, B s . , 59B, 529 (1926).

325. DziewBnski and Sternbach, Bull. Intern. Acad, Polonaise, C las se Sci. Math. Nat., 1935A, 333; - C. A., 30,2972 (1 936).



328. Freundler, Bull. SOC. Chim., [4], 9 , 735 (1911).

329. Freundler and de Laborderie, Bull. SOC. Chim., [4], 1 ,234 (1907).


331. Heller, Ber., 49, 2757 (1916).

332. Heller, Ber. , 55B, 2680 (1922).

333. Freundler, Bull. SOC. Chim., [4], 1, 228 (1907)

334. Freundler, Bull. SOC. Chim., [4],9, 778 (1911).

335. B a m b e r g e r , g , 4 4 , 1 9 6 6 (1911).

336. Arold, J. Prakt. Chem.,23, 329 (1964).

337. Heller, Ber. , 49, 546 (1916).

338. Carr6,Ann. Chim., [8], 19, 206 (1910).

339. Ca r r6 , Bull. SOC. Chim., [3], 35, 1275 (1906).

340. Carr6, Compt. Rend., 143,54 (1906).

341. Wessely, Schinzel, Spiteller, and Klezl, Monatsh. Chem., 90,96 (1959).

342. von Auwers and Kleiner, J. Prakt . Chem., 118,67 (1928).

343. F r i e s and Tampke,Ann., - 454,303 (1927).

344. F r i e s , Fabel, and Eckhardt,&, 550,31 (1941).

- -

- -

-

345.

346.

347.

348.

349.

350.

351.

352.

Spiteller and Wessely, Monatsh. Chem., 90, 660 (1959).

Witt, Nijlting, and Grandmougin, B s , 23, 2635 (1890).

F r i e s and Roth,&, 404,81 (1914).

Fieser , J . A m . Chem.Soc.,48,1097 (1926).

Zhao and Shchukina, Zh. Obshch. Khim., 29,3724 (1960).

Zincke and Kuchenbecker,&, 339, 235 (1905).

F r i e s and Weldert,&.,454,314 (1927).

Weygand and Henkel, B z . , 76B, 818 (1943).

353. Kovach and Barnes, J. Am. Chem. SOC., 76,1176 (1954).

354. Martsokha, Materialy-4-oi [Chetvertoi] Nauchn. Konf. Aspiriantov Sb, 1962, 106.

355. von Auwers and S c h a i c h , S , 54B, 1738 (1921).

375

Chapter 10

356. von Auwers and Frese,&.,450, 273 (1927).

357. von Auwers and A l l a r d t , s . , 4 3 8 , l (1924).

358. von Auwers and Demuth,&, 451,282 (1927).

359. von Auwers and Frese,=., 59B, 539 (1926).

360. von Auwers and Hiittenes,=., 55B, 1112 (1922).

361. von Auwers and Lohr , J. P rak t . Chem., 108,297 (1924)

362. Schad, - Ber. , 26, 216 (1893).

363. von Auwers and Dereser,=., 52B, 1340 (1919).

364. Syyder, Thompson, and Hinman, J. Am. Chem. SOC., 74, 2009 (1952).

365. Salkowski, - Ber. , 17,508 (1884).

366. Rousseau and Lindwall, J. Am. Chem. SOC., 72,3047(1950).

367. Pschor r and Hoppe,=., 43,2543 (1910).

368. Hayes and Hunter, J. Chem. SOC., 1941, l . 369. Hinman, Thesis , University oi Illinois, 1952.

370. Kochetkov and Dudykina, Zh. Obshch. Khim., 31,201 (1961).

371. Dudykina and Kochetkov, Zh. Obshch. Khim., 32,81 (1962).

372. Kirchner, U. S. Patent 3,007,938 (1959).

373. von Auwers and Lange, B z . , 55B, 1139 (1922).

374. von Auwers and Cauer,=., 61B, 2402 (1928).

375. P izz i and Ronchi. Gazz. Chim. Ital, 93, 3 (1963).

376. von Auwers and StrEdter,=., 59B, 529 (1926).

377. Hahn and Just , Ber. , - 65B, 717 (1932).

378. Borsche and Diacont,+,510,287 (1934).

379. Borsche and Bctschl i ,&E. , 522, 285 (1936).

380. V. Meyer,=., 22,319 (1889).

381. Dittrich and V. Meyer,Ann., - 264,129 (1891).

382. V. Meyer and SchulhEfer,&., 264,149 (1891).

383. Meisenheimer and D i e d r i c h , e , 57B, 1715 (1924).

384. Neber and Keppler, BE., 57B, 778 (1924).

385. Heller and Spielmeyer, - Ber . , 58B, 834 (1925).

386. von Auwers and Schwegler,%, 53B, 1211 (1920).

387. Tanasescu and Tanasescu,Bull. SOC. Chim., [5], 2,1016 (1935).

388. von Auwers and Allardt,=., 59B, 95 (1926).

389. Fischer and Tafel,Ann., 227,303 (1885).

390. Savitskaya and Shchukina, Zh. Obshch. Khim., 31,1015 (1961).

391. Ainsworth, J .Am.Chem. SOC., 80,967 (1958).

392. Re i s se r t and Grube, B ~ . , 4 2 , 3 7 1 6 (1909).

393. Kwartler and Lucas, J. Am. Chem. SOC., 65,1804 (1943).

-

376


394. Bamberger, - Ann., 305, 289 (1899).

395. Bamberger,&, 305,308 (1899).

396. Bamberger and von Goldberger,&., 305,339 (1899).

397. Bamberger and von Goldberger,&., 305,363 (1899).

398. Bamberger, B x . , 32,1773 (1899).

399. Hantzsch, - Ber., 35, 888 (1902).

400. Bamberger and von G o l d b e r g e r , K . , 31,2636 (1898).

401. Albert, Goldacre and Phillips, J. Chem. SOC., 1948, 2240.

402. Bamberger and Wildi, Ber., 39,4276 (1906).

403. Wiselogle, Survey of Antimalarial Drugs, Vol. 11, Edwards Brothers , Ann Arbor, 1946.

404. Parnell, J. C hem. Soc., 1959, 2363.

405. Fr ies and Tampke, Ann., 454,303 (1927).

406. Gabriel and Stelzner,&., 29, 303 (1896).

407. Fr ies and Weldert, - Ann., 454, 314 (1927).

408. Fr ies and Madjid, - Ann., 454, 311 (1927).

409. von Auwers and Schwegler,%, 53B, 1211 (1920).

410. British Patent 599 834, March 22, 1948; - C. A., 42, 7538 (1948).

411. Peticolas and Sureau, Bull. SOC. Chim. France, 1950,466.

412. von Auwers and Lange,%, 55B, 1139 (1922).

413. Himan, Thesis, University of Illinois, Urbana, Illinois, 1952.

414. Kwartler, U. S. Patent 2 478 048 to Winthrop-Stearns,August 2,1949;C. A., 44,3525 (1950).

-

415. Veselj. and Medvedeva, Collection Czechoslav. Chem. Commun., 9 ,176 (1937);=., 31, 5355 (1937).

416. von Auwers and Demuth, Ann., 451,282 (1927).

417. Witt, NElting, and G r a n d m o u g i n , z , 23,3635 (1890).

418. Fieser , J. Am.Chem. S O C . , ~ ~ , 1097 (1926).

419. Fabel, Thesis, University of Brunswick, Robert Noske, Leipzig, 1930.

420. Pearman, J. Chem. SOC., 119, 717 (1921).

421. Borsche and Diacont,&., 510,287 (1934).

422. Borsche and Scriba,&., 540,83 (1939).

423. Borsche and Biitschli, - Ann., 522, 85 (1936).

424. Noelting, - Ber., 37, 2556 (1904).

425. von Auwers and Frese,Ber,, 59B, 539 (1926).

426. Witt,Noelting, and Grandmougin, K, 25,3149 (1892).

427. Van Allan, J. Am. Chem. SOC., 69, 2913 (1947).

428. Brit. Patent 577,804 to Kodak Ltd., March 31,1946. C.A., 41, 1568 (1947).

429. Tillotson, U. S. Patent 2 374 791, May 1,1945; - C.A.,40,1636 (1946).

-

-

377

Chapter 10

Swiss Patent 242,054 to Aktien-Gesellschaft vom B. Siegfried, Sept., 1946; - C. A.,43,7966 (1949).

Rajagopalan, Current Science (India), 11,146 (1942);=., 36,6511 (1942).

Rajagopalan, Proc. Indian Acad. Sci., 18A, 100 (1943); C. A,, 38, 730 (1944). Lawrence and Goetchius, Proc. SOC. Exptl. Biol. Med., 58, 356 (1945).

German Patents 117,820 and 118,079 to Leopold Casella and Co.; Chem. Zentr., 1901, I, 488,551.

Kracker, German Patent 580,519, July 12,1933, to I.-G. Farbeindustrie; - C. A, , 28,1051 (1934).

Fries , Fabel, and Eckhardt, - Ann., 454,311 (1927).

Plazek and Neymanowna, Roczniki Chem., 12, 706 (1932); Chem. Zentr., 19331, 776.

CIBA Ltd., Brit. Patent 695, 330 (1953);C. - A.,48,4847 (1954).

Societ6 anon. de matieres colorantes e t produits chimiques Francolor, French Patent 981,432 (1951).

Peticolas, Sureau, Roe, and Develotte, U. S. Patent 2,675, 734 (1954). G., 49,1337 (1955).

430.

431.

432.

433.

434.

435.

436.

437.

438.

439.

440.

441.

442.

443.

444.

445.

446.

447.

448.

449.

450.

451.

452.

453.

454. 455.

456.

457.

458.

459.

Adams, Blinbridge, Bradley, and Davis, Brit. Patent 707,987;-., 48, 11804 (1954). Sureau and Blum, U. S. Patent 2, 795, 575 (1957);=., 51, 17178 (1957).

Davies and Legg, Brit. Patent 748,507 (1956); - C. A., 50,16115 (1956).

Davies and Legg, Brit. Patent 753,573 (1956); - C. A., 51, 7429 (1957).

Davies, Brit. Patent 747,871 (1956);%., 51, 8444 (1957).

Davies, Brit. Patent 760, 595 (1956); - C. A., 51,9168 (1957).

Davies, Brit. Patent 760, 710 (1956);%, 51,9168 (1957).

Petitcolas, Sureau, and Richard, French Patent 1,001,460; C. A., 51 18629 (1957). Sureau, Chimia (Switz.), 15,195 (1961).

Sureau and Kremer, French Patent 1, 211,449, (1960);-., 55,13863 (1961).

Sureau and Kremer, French Patent addition 77,666 (1962);=.,58,4671. (1963).

Sureau, Kremer, and Dupre, Belg. Patent 609,146 (1962);*, 59,1791 (1963).

Sureau, Mingasson, and Kremer, Belg. Patent 628,678 (1963); C. A., 61, 751 (1964).

Petitcolas and Sureau, Bull, Soc. Chim. France, 1950,466.

von Auwers and Kleiner, J. Prakt. Chem., 118,67 (1928).

von Auwers and HCttenes,=., 55B, 1112 (1922).

Paal and Lucker, - Ber., 27,447 (1894).

Zincke and Kuchenbecker,&, 339,235 (1905).

Fieser, J. Am.Chem. Soc.,48,1097 (1926).

-

378


460. Peti tcolas and Sureau, French Patent 1,005,327 (1952);=., 57,16561 (1957).

461. Peti tcolas and Sureau, Bull. Soc. Chim. France, 1954,986.

462. Synder and Williams, J. Am. Chem. SOC., 76,1298 (1954).

463. Ainsworth, J .Am. Chem. SOC., 79, 5242 (1957).

464. Ainsworth, J .Am. Chem. SOC., 79,5245 (1957).

465. Ainsworth, J. Am, Chem. Soc., 80,965 (1958).

466. Halvorson, Spiegelmann, and Hinman, Arch. Biochem. Biophys., 55, 512 (1955).

467. Davie, Konigsberger, and Lipmann, Arch. Biochem. Biophys., 65, 21 (1956).

468. Halvorson and Jackson, J. Gen. Microbiol., 14, 26 (1956).

469. Sharon and Lipmann, Arch. Biochem. Biophys., 69, 219 (1957).

470. Pardee , Shore, and P res t ige , Biochim. Biophys. Acta, U, 406 (1956). 471. Browerman and YEas,Arch. Biochem. Biophys., 68,112 (1957).

472. Frieden, Westmark, and Schor, Arch. Biochem. Biophys., 92,176 (1961).

473. Durham and Mart in , Biochem. Biophys. Acta, 71,481 (1963).

474. Adler, J. Med. Chem., 6,480 (1963).

475. Lingens, 2. Physiol. Chem., 331,56 (1963).

476. Hellman, Sell , and Wittwer, Phyton (Buenos Aires) , 16,1 (1961); - C.A., 57, 5057 (1962).

477. Heller and Spielmeyer, B z , 58B, 834 (1925).

478. Reis se r t and Lemmer , B x . , 59B, 351 (1926). 479. Behr, J .Am.Chem. SOC., 76, 3672 (1954).

480. Akashi, C. A., 43, 7934 (1949); Bull. Inst. Phys. Chem. Research. (Tokyo), 20, 798 m)

481.

482.

483.

484.

485.

486.

487.

488.

Tanasescu and Tanasescu, Bull. SOC. Chim. France, [5], 2,1016 (1935).

Secareanu and Lupas, Bull. SOC. Chim. France, [4], 53,1436 (1933). Secareanu and Lupas, Bull. SOC. Chim. France, [5], 1,373 (1934).

Secareanu and Lupas, Bull. SOC. Chim. France, [5], 2,69 (1935)

Bamberger and Demuth,=., 34,1309 (1901)

Bamberger and Weiler, J. P rak t . Chem., 58,333 (1898).

Sumuleanu, Ann. Sci. Univ J a s s y , 2,131 (1903); Chem. Zentr. , 1903II, 31.

Meisenheimer, Senn, and Zimmerman, BE., 60,1736 (1927).

489.

490. Noelting, Be r . , - 37, 2556 (1904). 491.


Bamberger and Wildi, B z , 39,4276 (1906).

492. Grandmougin and Freimann, J. Prakt . Chem., 78,384 (1908). 493. Pfannstiel and Ludde, Pha rm. Zentralhalle, 91,345 (1952); C. - A., 47, 7492

494. Serfass and Geppert , Monatsber.Deut. Akad. Wiss. Berlin, 4, 125 (1962); C. A., 59,4688 (1963). -

379

Chapter 10

Janssen, Proc. Intern. Meeting Mol. Spectry. , 4th, Bologna, 1959,2, 820 (1962).

O'Sullivan, J. Chem. SOC., 1960, 3278

Fischer , B x . , 13,697 (1880).

Fischer and Seuffert, B x . , 34, 795 (1901).

Heller and Jacobsohn,=,54B, 1107 (1921).

Pfannstiel and Janecke,=., 75B, 1096 (1942).

Stephenson, Org. Syntheses, 29, 54 (1949).

Fischer and Blochmann, B2,35,2315 (1902).

Gleu and Pfannstiel, J. Prak t . Chem., 146,129 (1936).

Purgotti and Contardi, Gazz. Chim. Ital., 32,I, 573 (1962).

Rupe, B z , 30,1097 (1897).

Kenner and Witham, J. Chem. SOC., 119,1053 (1921).

Kenner and Curt is , J. Chem. SOC., 105,2717 (1914).

Shunk and Wilds, J. Am. Chem. SOC., 71,3946 (1949).

Franzen and Eichler, J. Prak t . Chem., 78,157 (1908). Mentzer, Molho, and Berguer , Bull. SOC. Chim. France, 1950,782.

Thode, J. Prak t ,Chem. ,69 ,92 (1904). Heller and KEhler, Ber . , 56B, 1595 (1923).

Konig and Reisser t , B s , 32,782 (1899). Leonard, Boyd, and Herbrandson, J. Org. Chem., 12,47 (1947).

Stoll6, Nieland, and Merkle, J. P rak t . Chem., 116, 192 (1927).

Stollk, Nieland, and Merkle, J. Prakt . Chem., 117, 185 (1927).

Milrath, Monatsh., 29,909 (1908).


Heller, Ber. ,49, - 2757 (1916).



Freundler, Bull. SOC. Chim., [4],1, 228 (1907).

Freundler,Compt. Rend., 152, 1256 (1911).

Freundler and de Laborderie, Bull. SOC. Chim., [4], 1, 234 (1907).

Friedlznder and Lenk, - Ber. ,45,2085 (1912).

Murahashi and Horiie, Japanese Patent 8925 (1957);-., 52,14701 (1958).

Horiie, Nippon Kagaku Zasshi, 79,499 (1958);=., 54,4607 (1960).

Horiie, Nippon Kagaku Zasshi, 80,1038 (1959); C.., 55, 5510 (1961).

Murahashi and Horiie, U.S. Patent 2,949, 056 (1960);-., 55,1667 (1961). J.Am.Chem. SOC., 78,4816 (1956). Horiie and Murahashi, Bull. SOC. Chim. Japan, 33,88 (1960).

-

495.

496.

497.

498.

499.

500.

501.

502.

503.

504.

505.

506.

507.

508.

509.

510. 511.

512.

513. 514.

515.

516.

517.

518.

519.

520. 521.

522.

523.

5 24.

525.

526.

527.

528.

529.

530.

380


531.

532.

533.

534.

535.

536.

537.

538.

539.

540.

541.

542.

543.

544.

545.

546.

547.

548.

549.

550.

551.

552.

553.

554.

555.

556.

557.

558.

559.

560.

561.

562.

563.

564.

565.

566.

Fischer,&., 212, 333 (1892).

Veibel, Kjaar , and Plejl, Acta Chem. Scand., 5,1283 (1951).

von Auwers and Hii t tenes ,Bx. , 55B, 1 1 2 (1922).

Freundler , Bull. SOC. Chim., [4], 9 , 778 (1911).

Ullman and Bartkus, Chem. Ind. (London), 1962,63.

Pfannstiel and Liidde, P h a r m . Zentralhalle, 91, 345 (1952); C.A., 47, 7492 (1953).

Jennen, Ind. Chim. Belge, 16,472 (1951);C. A., 46,6387 (1952).

Jennen, Mededel. Vlaam. Chem. Ver. , 18,43 (1956);C.A., 51,5094 (1957).

Jennen, U.S. Pa ten t 2,673,801 (1954);=., 48,9850 (1954).

Wooley, Bri t . Patent 729 505 (1955);C.A., - 50, 712 (1956).

Gevaert Photoproducten N.V., Belg. Patent 514,576 (1933);=., 51,17542 (1957).

MacDonald, Mirzon, and Woolley, Brit . Patent 875,470 (1958).

Webster and Brooker , U.S. Patent 2,961,317 (1960); - C.A., 55,6221 (1961).

Jennen and Eerdekens, U.S. Patent 2,964,402 (1960);=., 55,9129 (1961).

Ba r r , Henn, and Salminen, U.S. Patent 3,043, 694 (1962); C, 57, 16048 (1961).

Ainsworth, Org. Syntheses, Col. Vol. II, 536 (1963).

von Auwers, Buschmann, and Heidenreich, Ann,, - 435,277 (1924).

von Auwers, von Sass , and Wittekindt,Ann., - 444, 195 (1925).

von Auwers, Conrad, Ernecke, and Ottens,&, 469,57 (1929).

von Auwers and Wolter, J. P rak t . Chem., 126, 204 (1930).

Kuehne, Weaver, and F ranz , J. Org. Chem., 29,1582 (1964).

Schlager, Arch. Pha rm. , 296, 758 (1963).

Mousseron and Manon, Bull. SOC. Chim. France, 1949,392.

F r i e s , Fabel, and Eckhardt, Ann,, 550, 31 (1941).

Wallach, - Ann., 329,109 (1903).

Grandberg, Kost, and Yaguzhinskii, Zh. Obshch. Khim., 29,2537 (1959).

Ainsworth, J . A m . Chem. SOC., 79,5242 (1957).

von Auwers and Kohlhaas, &. ,437,36 (1924).

von Auwers, Conrad, and Ernecke,&., 469,82 (1929).

von Auwers,&, 453, 211 (1927).

von Auwers and Wolter, E., 63,479 (1930).

von Auwers, Bahr ,and Frese,&., 441,68 (1925).

Mannich, Arch. P h a r m . , 267, 699 (1929).

Dieckmann,&., 317, 27 (1901).

Rabe and Eke,&., 323,83 (1902).

Rabe and Rahm, - Ann., 3 3 2 , l (1904).

-

381

Chapter 10

567. Kstz and Hesse,Llnn., 342,306 (1905).

568. Dieckmann and von Fischer, Ber.,44,966 (1911).

569. Lee and Christiansen, J . Am. Pharm. Assoc., 25,691 (1936). 570. Bradfield, Jones, and Simonsen, J. Chem. Soc., 1936,1137.

571. Ruhkopf, - Ber., 70,939 (1937).

572. Lee, U.S. Patent 2,104,348 (1938); - C.A., 32,1869 (1938).

573. Ruhkopf and Mohs, German Patent 668,628 (1938);=., 33, 5131 (1939).

574. Ruhkopf, Ber., 72,1978 (1939).

575. Picard, Seymour, and Dyer, Chemist and Druggist, 140,150 (1943); Quart. J. Pharm. Pharmacol., 16, 264 (1943).

576. Mousseron, Bull. SOC. Chim. France, 1947,612.

577. Skaric, Skaric, Turjak-Zebrik, and Veksli, Croat. Chem. Acta, 34,75 (1962); - C .A . , 58,4539 (1963).

578. Ruhkopf, - Ber., 70,939 (1937).

579. Ruhkopf and Mohs,German Patent 659,221 (1938);=., 32,5582 (1938).

580. De Stevens, Halamandaris, Wenk, and Dorfman, J. Am. Chem. Soc., 81, 6292 (1959).

581. Olsen and Aalrust,&.,648., 29 (1961).

582. Kishner and Sawadowski, J. Russ. Phys. Chem. Soc., 43,1132 (1911); Chem. Zentr., 19121,1456.

583. Kishner, J. Russ. Phys. Chem. Soc., 44,165 (1912).

584. Sussc and Gireiiiitscii, - Ber. , 63,2209 ii53Oj.

585. Grewe and Bokranz, Chem.=, 88,491 (1955).

586. Dimroth and Laewitz,Chem. Ber., 81,242 (1948).

587. Pocar, Bianchetti, and Maiorana, Gazz. Chim. Ital., 93, 100 (1963).

588. Wessely, Schinzel, Spiteller, and Klezl, Monatsh. C hem., 90,96 (1959). 589. Spiteller, Schmidt, Budzikiewiez, and Wessely, Monatsh. Chem., 91,129

(1960).

590. Dieckmann and Stein,=., 37,3370 (1904). 591. Crossley and Renouf, J. Chem. SOC., 101,1524 (1912).

592. Wichterle,Prochfizka, and Hofman, Coll. Czechoslovak. Chem. Commun., 13,300 (1948).

593. Smith, J. Chem. Soc., 1953,803.

594. Blaise and Koehler, Bull. Soc.Chim. France, [4], 7,710 (1910).

595. Knoevenagel and Heeren,=, 36,2124 (1903).

596. Huisgen, Seidel, Wallbillich, and Knupper, Tetrahedron, 17, 3 (1962).

- -

382

PART 4

Chemistry of Heterocyclic Compounds, Volume 22 Edited by Richard H. Wiley

Copyright 0 1967 by John Wiley & Sons, Ltd.

The following tables have been assembled into ten groups according to the nature of substituents on the pyrazole ring.

Group 1-Tables 1 to 22: Alkyl- and aryl-substituted pyrazoles.

Group 2-Tables 23 to 38: Carboxypyrazoles and their functional derivatives.

Group 3-Tables 39 to 49: Halogenopyrazoles.

Group &Tables 50 to 55: Nitroso and nitropyrazoles.

Group 5-Tables 56 to 62: Acylpyrazoles and pyrazolecarboxaldehydes.

Group 6-Tables 63 to 69: Aminopyrazoles and their derivatives.

Group 7-Tables 70 to 87: Hydroxy-, mercapto-, selenopyrazoles and

Group 8-Tables 88 to 89: Non-carboxylic acids and their functional

Group %Tables 90 to 94: Diazo, azo, azoxy, oxyazo, thioazo, hydrazino,

Group 10-Tables 95 to 110: Pyrazoles containing more than one r e p r e -

their functional derivatives.

derivatives.

azoamino and metallo-pyrazoles.

sentative function. The nature of t hese functions is indicated in the title of each table.

In each table the pyrazoles are arranged according to an increasing number of carbon atoms in the substituents which, in turn, are o r d e r e d as follows: alkyl, cycloalkyl, arylalkyl, a ry l and heterocyclic. Synthetic methods a r e indicated by roman numerals, sometimes followed by letters. The meaning of these symbols is explained in the following key.

385



KEY TO THE PREPARATION METHODS

I a

I b

I c

I d

I e

I f

I g

I h

I i

I j

I1 a

I I b

I1 c

I1 d

I1 di

I1 B I1 f

I11 a

111 b

111 c

I I Id

I V a JYb IVC

From P-diketones, with hydrazine and its derivatives (Ch. 3.1). From acetylenic carbonyl compounds, with hydrazine and i ts derivatives (Ch. 3.11). From a, P-unsaturated, Q -halo, a -alkoxy o r a -amino- carbonyl compounds, with hydrazine and i ts derivatives (Ch. 3. I) . From a, P-unsaturated, P-halo, 0-alkoxy o r p-amino-car- bony1 compounds, with hydrazine and its derivatives (Ch. 3.1). From ethyleneoxides or ethyleneimines carrying an acyl substituent, with hydrazine and i ts derivatives (Ch. 3. X V ) . By conversion of various heterocycles with hydrazine and i ts derivatives (Ch. 3.XIV). From f l -carbonylcarboxylic acid esters, with hydrazine and i ts derivatives (Ch.3.I). From 1, 2,3-tricarbonyl compounds, with hydrazine (Ch.3.IV). From 1,2,3-tricarbonyl compounds, with substituted hydrazines (Ch. 3.IV). From osazones and their derivatives, by dehydration (Ch. 5.VF).

From aliphatic diazo compounds, with acetylene derivatives (Ch. 3.VII.A). From vinyldiazomethane and i ts derivatives by internal cyclization (Ch. 3.VII. B). From aliphatic diazo compounds, with halovinyl- and nitrovinyl-derivatives (Ch. 3.VII. B). From aliphatic diazocompounds, with ketomethylene derivatives (Ch. 3.VII. C). From aliphatic diazocompounds, with malonic derivatives (Ch. 3.VIII. C). From tetrazoles, with acetylene derivatives (Ch. 3.VII.A). From sydnones, with acetylene or ethylene derivatives (Ch. 3.XVI).

By decarboxylation of pyrazole-1 -carboxylic acids (Ch. 5.VII). By decarboxylation of pyrazole -3-carboxylic acids (Ch. 5.VII). By decarboxylation of pyrazole -4-carboxylic acids (Ch. 5.VII). By decarboxylation of pyrazole-5-carboxylic acids (Ch. 5.VII).

By nitrogen alkylation or arylation (Ch, 4. IV). By carbon alkylation (Ch. 4. IV). By alkylation yielding pyrazolium salts (Ch. 4.IV).

387



Foreword to the Tables Section

V a

V a1

V b

V b l

V b2

V b3

v c

v c l

v c2

v c3

v c4

v c 5

V c6

v c7

V c 8

V d

V d l

V d2

V d3

V d4

V e

V f

v f l

v g

V h

By substitution of an a ry l or alkyl group with a hydrogen atom (Ch.4.IV). By substitution of an alkyl group with a halogen atom (Ch. 5.111). By substitution of an OH o r SH (OR o r SR) group with a hydrogen atom (Ch.3.XVII;Ch. 5.V-1X.a). By substitution of an SR group with a sulfonyl (SOi)

By substitution of a hydroxy group (or OR o r SR) with a halogen atom (Ch. 5.III-V-IX. C-X. B). By substitution of a hydroxy group with an alkyl o r a ry l - group. By substitution of a halogen atom with hydrogen (Ch. 5. I11 -V) *

By substitution of a halogen atom with a sulfonyl group

By substitution of a halogen atom with a OR o r a SR group (Ch. 5.III-X.B-X.C). By substitution of a halogen atom with a SO,R group

By substitution of a halogen atom with an amino group

By substitution of a halogen atom with a nitro group

By substitution of a halogen atom with a CN, SCN, o r COOH group (Ch. 5.111-VII). By substitution of a halogen atom with an alkyl o r a ry l group (Ch. 5.111). By substitution of a halogen atom with another halogen atom (Ch. 5.111). By substitution of a diazo o r of an azo group with a hydrogen atom (Ch. 5.VI). By substitution of a diazo o r of an azo group with a nitro- group (Ch. 5.IV-VI). By substitution of a diazo group with a halogen atom

By substitution of a diazo group (diazonium salt) with an azido group (Ch. 5. VI). By substitution of a diazo group with a hydroxyl o r an alkoxyl (Ch. 5. VI) . By substitution of a sulfonyl o r a sulfinyl group with a hydrogen atom (Ch. 5. X). By substitution of a COCl o r RCO group with a hydrogen atom (Ch. 5 . X ) . By substitution of a COOH o r RCO group with halogen atom (Ch. 5.111-VIII). By substitution of a phosphinic group with a hydrogen atom. By substitution of a Hg-X group with a SCN group (Ch. 5.11).

(Ch. 5.X.B-X.E).

(Ch. 5.111-X.E).

(Ch. 5.IJ.I-X.D).

(Ch. 5.III-VI).

(Ch. 5.111-IV).

(Ch. 5.111-VI).

388


V i V ii

VI a

VI 5

VII a

VII b VII c

VIII

lx

X a

X b

x c

X d X e

XIa

X I b

XI1

XI11

XIV a

XIVb

XIVC

By substitution of a nitro group with a halogen atom. By substitution of a nitro group with a hydrogen a tom (Ch. 5.IV).

S y oxidation of pyrazolines and pyrazolidines (Ch. 3 . X ) . By elimination of simple molecules from substi tuted pyrazolines (Ch. 3. XI).

F r o m hydrazonic halides with ketomethylene compounds (Ch. 3.X.A). F r o m hydrazonic halides with enamines (Ch. 3. X. B). F r o m hydrazonic halides with acetylenemagnesium salts (Ch.3.X.C).

Reactions on la teral chains which a r e not descr ibed in this work because considered as general organic react ions.

Decomposition of quaternary pyrazolium sal ts . (Ch.4.IV).

Rearrangement of pyrazolenines and of isopyrazoles (Ch. 3.XII). Rearrangement with dehydration of 4,4-dialkyl-5-hydroxy- pyrazoles. (Ch. 3.XIII). Rearrangement of 3, 5, 5-trisubstituted pyrazolines (Ch. 3. XIII). Rearrangement of dihydro-oxopyridazines. Rearrangement of thiadiazines to mercaptopyrazoles (Ch. 3.V).

F r o m aldehydes arylhydrazones with P-ketoesters in presence of zinc chloride (Ch. 3.VI). F r o m aldehyde arylhydrazones with phenylpropiolic acid (Ch.3.VI).

F r o m diazo-P-diketones o r f rom diazo e s t e r s with ketomethylene compounds (C h. 3. VIII) . F r o m acylphenylhydrazones of P-dicarbonyl compounds with alkaline condensing agents (Ch. 3.111).

F rom aromatic diazo derivatives, with compounds which can undergo coupling at a position p to a carbonyl group (Ch. 3.IX; Ch. 5.V). F r o m diazonium sa l t s and furan o r pyrrole der iva- t ives (Ch. 5.VIII). F r o m P-arylazofurans and pyrroles, with hydroxylamine (Ch. 5.VIII).

389


xv

XVI

XVII a

XVII b

XVIII a

XVIII b

XVIII c

XVIII d

XVIII e

XIX a

XIX b

XIX c XIX d XIX e XIX f XIX g

X X a XX b

XXI a XXIb XXI c XXI d XXI e XXI f

= g

XXI h

XXII a

F rom malonic e s t e r , with arylazides (Ch. 3.VII. C).

F rom halogenocarbonyl compounds with mono - and dithio - carbohydrazides. (Ch. 3.V).

Oxidation of lateral chains to carboxyls (Ch. 5. I; Ch 4.VII). Oxidation of a substituted methylene group to a keto group (Ch.4.1; Ch. 5.VIII).

Rearrangement of an alkyl group f rom a ring nitrogen atom to another (Ch.4.W). Rearrangement of an acyl o r of a carbethoxyl group from a ring nitrogen atom to another (Ch. 5 .X) . Rearrangement of a carbamido group from a ring nitrogen atom to another (Ch. 5 . X ) . Rearrangement of a nitro group f rom a ring nitrogen atom to a ring carbon atom (Ch. 5.IV). Rearrangement of a nitroso group f rom a ring nitrogen atom to a ring carbon atom (Ch. 5. IV).

Halogenation by halogens, IC1, NaOC1, NaOBr, SO,Cl, and PC1, (Ch. 5.111). Nitration by nitric acid, ni t r ic acid-sulfuric acid mixtures and nitric acid-acetic anhydride mixtures (Ch. 5. IV). Nitrosation by nitrous vapors (Ch. 5.IV). Coupling with diazonium sa l t s (Ch. 5.IV). Sulfonation and chlorosulfonation (Ch. 5. X. E) . Reactions with S,C1, and SC1,. Mercuration reactions (Ch. 5.11).

Halogenation of aminopyrazoles. Halogenation of pyrazoleselenones o r of pyrazoledisele - nides (Ch. 5. X. F).

Oxidation of the nitroso group (Ch. 5.IV). Oxidation of the hydroxylamino group to nitroso group. Oxidation of the hydroxylamino group to azoxy group. Oxidation of an amino group (Ch. 5.V). Oxidation of a hydrazo group (Ch. 5.V). Oxidation of a -SH (or SeH) group to S-S(or Se-Se)

Oxidation of a -SR (or SeR) group to SO,R (or Se0,R)

Oxidation of a -SH (or SeH o r SeR) group to SO,H (or Se0,H) (Ch. 5.X.E-X. F).

F rom nitrosopyrazoles, with compounds containing active methylene groups (Ch. 5. IV-VI).

(Ch. 5.X.C-X. F).

(Ch. 5.X.B-X.D-X. F).

390


X W a1

XXII b

XXIII a XXIII b XXIII b l XXIII c XXIII c l

X W I d XXIII e XXIII f XXIII g XXIIIh

XXIV a X X N b

XXVa

XXVb

xxv c

XXV d

XXVe

XXV e l

XXV e2

xxv f

XXVI a

XXVI b XXVI b l XXVI c

XXVI d

F r o m aminopyrazoles, with aldehydes or ketones (Ch. 5.VI). F r o m aminopyrazoles with nitrosopyrazoles (Ch. 5. IV-V) . Reduction of NO, to NO (Ch. 5. IV). Reduction of NO, or NO to NH, (Ch. 5.IV-VI). Reduction of NO, or NO to an azo group (Ch. 5.IV). Reduction of an azo group to an amino group (Ch. 5.V-VI). Reduction of an azo group to an amino group followed by semidinic rearrangement (Ch. 5. VI). Reduction of an azo group to a hydrazo group (Ch. 5.V). Reduction of -SO- or of -SO,- to -S-. Reduction of a -S-S- group to a thiol group Reduction of a -COC1 ProuI) to -CHO (Ch. 5.VIII). Reduction of a -S02ClY(or ̂ SO,R) group to -SO,H (Ch. 5. x-XI).

Hydrolysis of a -CC1, group (Ch. 5.VII). Hydrolysis of a -dihalogenated alkyl groups (Ch. 5. VIII).

Nitrogen acylation of magnesium or lithium pyrazoles with chlorocarbonates. Reaction of magnesium or lithium pyrazoles with carbon dioxide (Ch. 5.11-VII). Reaction of magnesium or lithium pyrazoles with acyla- ting agents (Ch. 5.11). Acylation at positions 1 or 5 by sulfonic, sulfinic or sul- fenic halides. (Ch. 5 . X ) . Acylation at positions 1 or 4 by acid halides or anhydrides

Nitrogen acylation by acyldiazomethane, followed by heating or U.V. irradiation (Ch. 5. XI). Formylation a t position 4 with a dialkylformamide and phosphorus oxychloride (Ch. 5. VIII). Nitrogen acylation by chlorocarbonates and isocyanic acid e s t e r s (Ch. 5.VII). F r o m pyrazole -3 -carboxylic acids, on treatment with acid halides (Ch. 5.VII).

(Ch. 5. VIII-IX. B-XI-X. D).

By alkylation o r acylation of pyrazolones, pyrazolethiones or selenopyrazoles (Ch. 5.VIII-1X.A-IX. B-IX. C-X.A-

By alkylation or acylation of aminogroups (Ch. 5.VI). By alkylation of pyrazolonearylhydrazones. Rearrangement of an acyl group from nitrogen to oxygen in N-acyl-pyrazolones (Ch. 5.IX. B). Rearrangement of an alkyl group from nuclear nitrogen to sulphur, selenium or to non-nuclear nitrogen in N - alkyl-pyrazolethiones, selenopyrazolones o r aminopyrazoles (Ch. 5. VI-X. B).

X. B-X. F).

391


XXVI e XXVI e l

XXVI f

XXV1l a

XXVII b XXVII d

XXVII e

XXVII h

XXVIII

Alkylation of -SO,H groups to -SO,R (Ch. 5.X. D). Pyrazole ketones from acid chlorides o r from es te rs of pyrazolecarboxylic acids (Ch. 5. VIII). From pyrazolones or from aminopyrazoles, with isocyanic, isothiocyanic es te rs or with carbon disulfide

From nitrosopyrazoles with alkalies (Ch. 5. IV). From pyrazolediazonium salts with alkalies (Ch. 5.VI). By hydrolysis of groups joined to amino nitrogen (Ch. 5.VI). From pyrazolecarboxylic es te rs o r amides with hydroxylamine. From diazopyrazoles, with mineral acids (Ch. 5. VI).

From Q -dicarbonyl compounds with hydrazinoacetic acid derivatives (Ch. 3.111. B).

Literature references relate to synthetic methods indicated on the

Among derivatives a re reported functional derivatives and salts.

same line. Boiling and melting points a r e in centigrade degrees.

392

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CH

2CH

2CH

3

13

CH

,CO

CO

OH

Ia

B

. 13

6-13

7"/7

47

25

IV a

B

. 66-

70"/

0.7

986

VII

I

VII

I

VII

I

IV a

VII

I

Ia

VII

I

519

519

519

M. 1

64-1

66"

51

9

519

B.

166-

167'

,"75

5 25

974

Pic

rate

: M

. 135

-136

"

Die

thyl

acet

al: B

. 11

2-11

9"/2

3

2,4

-din

itro

ph

enyl

hyd

razo

ne

M. 1

73-1

73.5

"

'2H

C1:

M.

120-

130"

Dip

icra

te: M

. 176

-178

"

.2H

C1:

M. 1

20-1

30"

Dip

icra

te : M

. 162

-164

"

'2H

C1:

M.

130-

140"

Dip

icra

te : M

. 17

5-17

7"

Eth

yl e

ste

r: B

. 13

0°/2

0

Am

ide:

M. 1

51-1

53"

Met

hyl

amid

e: M

. 11

0-11

1"

Dim

eth

ylam

ide:

M.

112-

113"

Pic

rate

: M

. 99-

100"

Eth

yl e

ste

r: M

. 74

-75"

W

W

UI

,CO

OH

14

-C

H,--

CH

N

atu

re

IV a

(?

)

VII

I

WH

,

15

CH

,CH

,CH

,CH

, I

a

I11

c c, d

Vb

f

VIa

b

M. 2

36-2

38"(

d)

395,

792

39

5,7

92

M. 2

43-2

44"(

d)

986

B.

174-

175"

/745

25

.

B. 8

1-82

"/3

0

863

5

B. 2

55-2

57"/

750

515

B.

134-

135"

/15

M. 2

02-2

02.5

"

507

507

B.

246-

247"

38

1

B.

107"

/7

267

B. 7

4"

/0.0

5

48

9,1

00

9

572

266

977

74

44

0

31

,84

8

Ace

tyl

der

iv. :

M.

153-

153.

5"

Nit

rile

Pic

rate

: M

. 77-

78"

Dim

eth

yl e

ster

: M

. 13

9"

M.

158"

-AuC

13

HC

1: F

. 1

80

.5-1

81

.5"

-14P

tC1,

.HC

l . l

,$Pt

C1,

. l

,$H

,O

m W 0 r3

Ln

\

N w 3

I W m 3

0

0

a

cd CI

m X 0

?j 0 cy

m W 0 3

Ln

\

0 0 4 3 I

0

k a m * 2 scd

cd CI

.-I + 3 cu

4 N 0 0 3 m m

m m I

W W

2

4 0 w w m e ¶

Ln m I

4 m

Ln

s

N

2

3 3 W W m

0 N c- 3

0 0 I w o 3 w c - f - 3 3 3

s s s

Q N N

m N x

2 I

Q

Ia

M

. 41"

10

83

c1

B.

118-

120"

/2

Ia

M

. 10

7-10

9"

38

1,1

07

9,1

13

1,1

13

2

d M

. 10

9-11

0"

85

0

B. 2

46

,5"

/75

4.1

10

6 28

5

**

M.

32

,5-3

3"

10

6

29

ec

n3

**

VIB

B

. 258

-259

"/75

6.9

380

Ia

M

. 13

8-13

9"

28

VII

I M

. 14

0-14

2"

28

,10

7

31

-@

eon

VII

I M

. 26

4-26

5"

107

32

VII

I M

. 11

6-11

7"

382

4

W

w

33 QQ

c1-

1

13

3

.HC

llg

PtC

l, : M

. 2O

O-2

0lo(

dec.

)

.HC

1 . l

hPtC

1, : M

. 18

3-18

4"(d

ec.)

Hy

dra

zid

e : M

. 13

5-13

7"

Eth

yl

est

er:

B.

308-

310"

Eth

yl

est

er:

M.

61-6

2"

~H

~C

H~

OH

* F

rom

ep

ich

loro

hy

dri

n w

ith

ph

eny

lhy

dra

zin

e **

Fro

m e

pic

hlo

roh

yd

rin

wit

h 0- o

r p-

toly

lhy

dra

zin

e

T-4

BL

E 2

. 3(

or 5

)-A

lkyl

- or

Ary

l-su

bst

itu

ted

Py

razo

les

H

CD

m

w

H aq'

I B M

eth

ods

Ref

eren

ces

Der

ivat

ives

N

. R

of

sy

nth

esis

M

.p. o

r B

.p.

1 C

H,

Ia

b

c d

I1 a

b

I a-

I11

a

2 C

H,C

1

I11

b

C

Va

VIa

b

* VII

I

M. 3

6-37

"

23

8,3

97

,54

7,5

48

,78

7,7

88

B. 2

04"

/7 5

2 8

92

,89

4,1

08

8,1

14

0

B. 2

00"/

748

1017

,101

9

B.

108"

/25

1016

,101

9

25

,57

7,

787

862

296

1018

,101

9,10

25

58

,30

0,3

01

,62

7,6

29

829

247,

248

439

1019

351

M.

155-

156"

51

5,11

35

.AgN

O, : M

. 121

"

'3H

gClZ

: M.

165-

168"

.PtC

1, :

M. 2

53"

.2H

C1.

PtC

1,

.2H

z0

: M

. 18

1"

Ag

salt

Pic

rate

: M

. 142

-145

"

Pic

ryls

vlfo

nat

e: M

. 216

-217

.5"

-(C

l--@

0,)2

. NH: M.

13

4-3

5'

3 C

H,O

H

4 C

HZ

OC

H,

5 C

H,N

H,

6 C

HZ

CH

,

7 C

XC

H

8 C

HzC

HO

9 C

HZ

CO

OH

Ib

I1 a

VII

I

I1 a

VII

I

Id

VIa

V

III

I1 a

If

VII

I

B. 1

37-1

40"

/0.5

B. 70" /o

. 1

B. 1

07-1

08"

/15

B. 9

0"/1

2

M. 4

5-46

"

B. 8

6"/4

M. 10

7-10

9"

B.1

06

"/0

.4

518

515,

1136

515,

1135

862

583

25,3

87

297

29 7

297

518,

1142

515,

518,

1135

10

CH

ZC

HZ

NH

, VIII

B. 1

20-1

30"

/0.5

51

5,51

8

B.1

18

-12

3"

/0.5

w

W

(D

*"F

rom

3-m

eth

ylen

pyr

azol

ine,

dro

ppin

g it

on

a m

ixtu

re o

f K

OH

, Ag,

Pt,

hea

ted

at

200"

'HC

1: M. 1

17-1

18"

Pic

rate

: M. 1

81-1

82";

184

-185

"

Pic

rate

: M

44"

Pic

rate

: M

. 127

,5-1

28"

; 12

9"

Pic

rate

: M

. 122

-124

"; 1

26-1

27,5

"

Hyd

razo

ne:

M. 1

22-1

23"

+HC

1: M. 1

16-1

17"

; 13

7-14

0"

Eth

yl e

ster

: B. 1

06" /

O. 4

Eth

yl e

ster

.HC

I: M

. 107

-109

"

Am

ide:

M. 1

48-1

49"

Nit

rile

: B

. 117

-120

"/0

.4

Nit

rile

-Pic

rate

: M

. 63-

64"

.2H

C1:

M. 2

24-2

27"

Dip

icra

te : M

. 195

-197

"

h

B 0 v

N

w ;1 m 2

w 3

3 0 1 w N 3 3 N 3

W 3

Ln

i?

\

0 m N

I 0 C Y N

0

a

3 3

w L n 3 1 - w 3 3

m 3

3

a,

k u

E

00- Ln

C - N Z G

m 0 w

0 w d

ri 1 3 I

2 3 ... Ln

cd 0 3

Ln I

2

0 CO W 0

I 3

w ?+ C- W

a, a, d 0

* * 2 )i: 6

d P CI

mm : : u

N 3

t- 3

W 2 , " 4 n ?+

400

m w I

w

3 W I 0 W

I m In

03 ln

I

m t-

I w m

I

0 w W

2 3 W

s t- m

rj 2 0" z, ..

c 2

W

f 3

0 0 m 3 I

3

f- W 3

I h N 3

zi

mm u 2

2 mN

h

u

u v

h

2 2 u

u v

h . N m u

u

v

2

m w N N

3 N N N

m o 3 N

m 3

f- N

m W N N

40 1

q v 8

W !J m

p: 2 I 2

N m 3 W W m

m m I

Fu m

s

3 m m mi N

W co W

W

3 3

In 3

I In

L- Q,

o In 3

i

a 0 3 CII m m m ca

402

33

-CH

,(C

H,)

,CH

, M. 88. 5-89.5"

862

34

C,H

, I

a

M. 72-74"

b M. 78-79"

C

B. 310-315"

d

B.

200"

/20

f B. 177-178"/11

I1 a

1 a-111 a

I11 b C

b, c

11

1 c-

V

a

VIa

Vb

V f

-VI

a

WIa

VII

I

Id

M. 89-90"

Pic

rate

: M. 169"

213,550,552,558

Ag s

alt

: M. 85"

192

342

.HC

1: M. 144-145"

542,581

541

535

Pic

rate

: M. 16

8-171"; 177-178"

121

216,550,955

308

212,552

463

.HN

O, : M. 126"(dec.)

.HC

1 .

lhP

tC1,

. H

,O:

Dec

. 193" M

. 218"

162

454

213,439

21

581

Id

M. 98"

581

TA

BL

E 2

(co

ntd

)

rp 0

rp

Met

hod

s N

. R

of

sy

nth

esis

M

.p. or

B.p

. R

efer

ence

s D

eriv

ativ

es

38

39

*C

H.

40

~O

CH

~C

H~

CH

~

41 O

OC

~H

~

42

G

4

3

4=&02

Id

M

. 127

"

Ia

M

. 98-

99"

VIa

M

. 126

"

Ia

M

. 80"

b

I11

b

VIa

B

. 256

"/11

Id

M

. 120

"

Id

M

. 19

2-19

3"

Vf

il

VII

I

581

1077

,110

3,11

04

452

846

846

846

452

581

581

310

310

21

3,3

10

,55

3,7

69

'HC

1: M

. 158

-164

"

Pic

rate

, M.

127-

128"

*H

N0

3: D

~c

. 182-

184"

M.

128"

4 N

0 In N I-4

s

u Y

0,

rD t-

m- 3 N

N 4 > 0 0 m

r" z I

p \ Q Q w In d. w

cc) I-4

N

Y l-,

ji

(0 W

I-4 N

0 m W 3

z;

Y

s"

I z, m

f- w

w

3 2 t- t- 0 I-4

& In 3

t- v) 3

I

s

ol Y

m

P-

2 4

t- 0 3

0 N ua 3 I 0 In 3

s

cd U

0 In

03 Q, v W

405

m Q, 3

,i W cd U

*

ii:

N m *

0 3

b 0 Q, 3

I co 03 i

a

N

s

" X

% Y

8

2 "

m

&I 0

4 d

s

ea m w

3 3 >

a

m W 3

cd

F

N - E" u I X V

l-4 N m m

0 c- c- N

si:

1 s

.. W Y

0

m m m m

rl i

w w w w * m m 3

0 m

I

m i

3

In 3

2

m W m m w In W m m

406

TA

BL

E 3

. Q-Alkyl- or

Ary

l-su

bst

itu

ted

Py

razo

les

N.

R

Met

hod

s of

syn

thes

is

M.p

.or

B.p

. R

efer

ence

s D

eriv

ativ

es

1 C

H,

2 C

H2C

1

3 C

H20

H

Ia

d

111

b

I11

b,d

-VII

I

VIb

VII

I

I1 a

Va

VII

I

Ia

d

111

b

M. 1

5.8

-18

.5"

84

7,10

65

AgN

O, : M

. 142

"

B. 2

04-2

05"

20

2 P

icra

te : M

. 142

"

B.

107-

109"

/16

515,

793,

828

B.

95"/

13

278

B.

70-7

3"/3

84

1

515

M. 1

26-1

27"

51

5

515

515

B.

122"

/16

847

B. 1

04-1

05"

/3

202

B. 8

2-85

"/3

25

Pic

rate

: M

. 14

9-15

Oo(

d.)

Pic

rate

M. 1

30-1

35";

137

"

0 0 m rl

I Q) cu rl

z4 G x ..

co rl m

z s

2 x

x u

m

co rl m

0 m m I * m

A

W U

3:

3:

x V

ON

W

0 co cu cu

I

0 W rl rl I

m rl rl

2 .. G T

P c o m * A cu c o r n

U

" F f: U U U

408

0 m 0 rl I

w 5: ri G ?

..

C O W r l r l m m

0 0 0 0 m m m rl rl rl

m m r ( r l m r l rl rl rl

c- 0 L n

rl m

e, 0

m 0

0 \

$ $ % ! g

I W m rl

A

rl N N

ri r i i

0

3 0

3 w rn

N

ti- N - n

X X ON X u, % X u

3 N

40 9

TA

BL

E 3

(co

ntd

)

Met

hod

s of

N

. R

sy

nth

esis

M

.p. o

r B

.p.

Ref

eren

ces

Der

ivat

ives

22

C,H

, I

a

M.

230-

231"

f

I1 a

I11 by

d

b

I11

by d

-VI

a

Vd

VIa

b

847,

906

Ag

salt

54 1

-H

Cl:

M.

215-

218"

535

209,

210,

215

Pic

rate

: M

. 15

5"

554,

829

210,

219,

221

816

210,

220

93

*HC1: 1

/2P

tCI,

: M

. 287

"(d

.)

1 1

m .b c)

.f 4 B P

co m 3

!n

a

9

411

& m I m I-

I 0

2 N In 3

5: i

2 4 &

3

a,

0

3

m m

N 3 3 In m - 8 0 2 m

m m m a Q)

m m m m m 0 4 m r n

m 0

2 I- * a

d i V

d V

W

n

N m m 2 3 3 3

* * 3 m

TA

BL

E 4

. (co

nt.)

N.

R

R’

Met

hod

s of

sy

nth

esis

M

.p.

or B

.p.

Ref

eren

ces

Der

iva

tiv

es

t- L- 3

W L- ?-I

I

rn oo

m

il

a,

il

Y Y

ii: ii

I

413

p:

3 m

0 m Q1 nr r m I i l x N N

z? u N m

414

3 ..

415

m 4 1

w w w w w w w w E - m w * * w * * * w ca m m m c o w m c o m c o m 3

E- 3 3

I W 3 3

J

s * 3

i

s 4 3

9 c) N 3

i

& 0 4

I m 2 i

b 3 3

z-

m

m' m

i & m

J

m UY 3

m UY 3

i

B V

N L n

416

3

3 W

b m 3

2

3

Y X'

0 d

b m 3

I 00 n 3

i 5: .- a, 5

x 3 c

s

- Y 5

n N k

i

c- in 3

d Y

3 W

417

I J

i 3

L- m * n m (D

8 m *

c' c) 3

m N N

* 01 N

I

i i

d d CI 3

* (D m W

N m N 0 0 3

N 0

2

m c) rl

i N (D 3

i

L m I

d

m m 3

i

rd d rd d

3 H 3 : s

G V

m W

2 Ern v v

v) W * W

3

t- (D 3

cd

418

8 i i

f

n

0-

m- m

m-

N i i

0 i *

t-

N

H m L-

N t - n t- t-

w n" m t -

n m

m- "

L-

w N m w

N m

L- m

M

m i

z!

k cr i

z!

'CI CI

w ci

id ci

2 V

i L-

m X V

2 V

m L- m t- cr t- W t- L- t- N L-

419

m 3 In

F

In 0 i

i

m m

N m

3 m

0 m w In

m m

420

b In

L 0 N

i W Y

2 ir,

" E- m

m 2

8

Y

c .3

4

* R

a s

m E- m

m N 3

b m & 3 m 3

i i m

w 7 n

E 64 E

0-v)

2" I

0 m

* E- E-

N o w d m

& Ln 3

m m 8 8

* Q, m m m m

42 1

TABLE 4

. (co

nt.

)

Met

hod

s of

sy

nth

esis

M

.p. o

r B

.p.

Ref

eren

ces

Der

ivat

ives

N

. R

R

' * N

N

yC

H3

-C

H=

CH

al

n

ow

96

It

I

1

If

M

.154

-155

"

774

H

&H

I

C6

H5

I

97

<H,C

--C

H=C

HC

,H,

C,H

, I I OH

98

C,H

,

99

C,H

,

100

C,H

,

C6

H5

Ie

Ia

b

C d

I a-

III

a

I c-

I11

a

I d-

IX

a

VIa

b

VI

a-V

f

*

M. 1

78-1

81"

60

8

M. 1

99-2

00"

1

1,3

40

,61

0,5

67

,90

2,1

04

4

.HC

1: M

. 232

-233

"

M .2

04

"

746,

747

Pic

rate

: M

. 161

-163

"

B. 3

47"/

155

2, 3

42

Com

poun

d w

ith

1,3

,5-

B. 3

17"

/160

3

3,3

4,7

3,5

67

,90

2,1

04

4

trin

itro

ben

zen

e:

84

5,9

02

,10

44

M

. 135

.5"

342.

866

2,8

45

,90

2,1

04

4

439

1036

,103

7

454

406

Ia

M. 1

44"

10

4

Ia

M

. 159

-160

"

523

b

M. 1

63"

746,

747

VI

b

40

6,5

23

w OI

m 0 m m

W L!am m c n 2 2 % El 2 3

cn Ln

L!Y

3

El

i n n in =: :- u =a =a u v

423

w m w c u w m

b K

$ 8 i i

w m a 3

N 3

r d r d w w

0 3 N N 0,

3 3 3 3

m 3 3

r 3 3

m + 2 2 s N

i l z 3 3 3 3

8 m

rd CI

Q

N N 3

424

t - t - t - t - P t -

n w 3

s

d w CI

t - t - c - t - t - t - t - t - t - t - t - t -

In N N

I w N N

& 0 N

I m m 3

s s

r d w d w

ar” CI

In 3 m

w m 3

s E’ rd d

7 ! CI CI

E

n N 3

w N -

?YS ‘4

s In N 3

y. u=u

I =

(D N 3

t- N 3

TA

BL

E 5

. 3,

4-A

lkyl

- or

Ary

l- D

isu

bst

itu

ted

Py

razo

les

N.

R

R' M

eth

ods

of

syn

thes

is

M.p

. o

r B

.p.

Ref

eren

ces

Der

iva

tiv

es

1

CH

, C

H3

Ia

ma

2 C

H,

CH

,CH

,CH

, II

c

4 C

H,

C6

H.5

I

a

III

b

VI

b

VII

I

5 C

H,

6 C

H,

-(-J

If

M. 5

5-58

'' 2

5,7

4,3

33

,79

3,1

06

5

Pic

rate

: M

. 153

"

B. 1

11"/

10-1

1 10

25

B. 1

21'Y

lO

817

.HC

I: M

. 17

1"

Pic

rate

: M

. 104

"

B. 1

02-1

03"/

11

50

M. 1

40-1

41"

1

7

Pic

rate

: M

. 15

5"; 1

58-1

59"

0.0

05

817

737,

817

17

M. 1

20-1

21"

1

5,1

8,1

9,2

0

.2H

C1:

M. 2

50-2

52"

.HzS

O,:

M

. 266

-268

"

Pic

rate

: M

. 19

1-19

2"

cu m rl

N 0 3

I

s

P- 3

m cu 3 I

-F cu rl

>

a

In rl

d E I * U P W

0 m 3

W : F U

3 cu 3 rl

0 rl

m -F rl 3

L n 3

427

h

Y c 0 V Y

m' w d m 2

m 9* m

a m m l-l

N m d

I

N h m

z = O Y I'

I

W rl

m -# m

d

I

0" z N n m

co rl

W d

w H

N h

x" V 3: CI

3 u

0 N

I m L- d

m W -#

5 W

m

zi

d Y

z - V

rl N

42 8

m 0 N

w 0

P

El

m 5: V

0 m rl

W 4

rl W rl

0 Ln Ln rl

I w m rl

I

i r’

LD

% V

z? U

V In @ g V

N N

-3 N

m N

% 3

m I

c*) m 4

r’

4 V

m N

W N

I

42 9

TA

BL

E 5

.kon

t.I

* 0

w

Met

hod

s of

N

. R

R

' sy

nth

esis

M

.p. o

r B

.p.

Ref

eren

ces

Der

ivat

ives

32

-CH

2CH

2CH

2-

Ia

IIIa

b

3 3

-CH

,CH

2C

H(C

H ,)-

IIIa

36

XH

ZC

H2C

H2C

H2-

I

a

IIIa

M. 1

27-1

27.5

"

M. 1

45-1

46.5

"

M. 5

7-59

"

Oil

Oil

M. 8

9-90

"

M. 8

4"

B.

151"

/14

498

502

9 'H

Ck

M. 2

03.5

-204

.5"

1025

P

icra

te:

M. 2

38.5

"

86

1025

.H

C1.

P

t C1,

1025

.H

C1.

'h

P

tC1,

1025

'H

C1.

1/2

PtC

1,:

M. 2

20-2

22"

1025

9,10

65

Ag

sa

lt

1025

.H

C1

IV a

vm

c1

37

)C(O

H)C

(OH

)2C

C1=

CC

1-

VII

I

38

XH

,CH

(CH

,)C

H~C

H~-

I

a

ma

39

-CH

,CH

,CH

(CH

,)CH

,- II

Ia

40

-CH

,CH

(CH

,)CH

,CH

(CH

,)-

I a

-m a

m

a

/CH

3 41

-CH

(CH

S)C

H~C

H~C

H-C

m

'

pC

H2

42

XH

(CH

~)C

H~

CH

~C

H~

- I

a

I a-

III

a

(cH

,),=c

H

W *

43

>CH

CH

,CH

,CH

(CH

~)-

III

a

44

XH

(CH

,)CH

,CH

,CH

'' 11

1 a

c..

CH

(CH

3),

\

446

409,1151

M. 155-160°(d)

408

M. 99-100"

1025

1025

M. 74

-75.

5"

89

B. 168"/20

M. 76-77"

89

B. 151-152"/10

89

Oil

1025

B. 152.8"/12

57

57

Oil

Oil

1025

1025

.HC

1. '1,

Pt C

1,

.Pic

rate

: M

. 155-156"

.l/2A

gNO

,: M. 137-139"

Pic

rate

: M

. 136-138"

.HC1

Pic

rate

: M

. 156-157"

Pic

rate

: M

. 167-168"

.HC

1. l/Z

P

t C1,:

M. 201"

Ag

sal

t

.l/Z

AgN

O,:

M. 132"

.HC

1

Pic

rate

: M. 151-152"

.HC

1. 1/

2 PtC

1,:

M. 216"

.HC

1. '/2

PtC14: M

. 226-228"

TA

BL

E 5

. (co

nt.)

N.

R

45

46

47

48

Met

ho

ds

of

R'

syn

thes

is

M.p

. or

B.p

. R

efer

ence

s ._

- -

~ - -

~~

__

__

~_

__

~

__

D

eriv

ativ

es

- %"'..$ H-

C(C

H

I - (

C€1

3)-

CH

zCH

2-

Q

1025

.HC

1. '12

Pt C

l,:

M. 188-190"

I a-

III

a O

il

III

a M

. 149-150"

1025

.HC

1. 1/2 P

t C1,

Ia

I a-

III

a

Ia

IIIa

Ia

Ia

M. 135"

9

M. 123"

96

B. 212-213"/11

Pic

rate

: M

. 102-1 93.

M. 66-67"

223,224,1003

.HN

O,: M. 144"(d)

1025

.HC

1. 1/2 P

t Cl,:

M

. 238-239"

M. 106.5-

1003

10

7.5

"

M. 114-115"

224,1003

B. 149-151"/

0.01

3,4

-Ste

roid

o-P

yra

zole

s

Met

hods

of

R""'

, sy

nth

esis

M

. p.o

r B

.p.

Ref

eren

ces

Der

ivat

ives

R

t R

" R

"'

R"

1H

H

H

OH

H

H

Ia

M

. 248

-251

.5"

275

a

2 H

H

H

O

H

CH

,CH

, H

I

a

M.

149.

5-15

0.4"

27

5 a

3H

H

H

OH

H

CH

, I

a

275

a

.C,H

,OH

. M

. 1

27

.6-1

28

.47

21

7-22

5"

4 H

H

H

O

H

CH

, C

H,

Ia

M

. 22

9.8-

242"

27

5 a

N-a

cety

l de

riv.

: .C

,H;O

H:

M. 11

1.4-

115.

4"

N-p

ropi

onyl

der

iv.:

M

. 13

4.4-

14

8"

N-(4-chlorphenoxyacetyl) de

riv.

: M. 1

64.8

-167

.6"

5 H

H

H

O

H

CH

ZC

H,

CH

, I

a

275

a .C

,H,O

H:

Sy

nte

r. 1

40-1

50";

M

. 249

-51"

* W

w

6 H

H

H

O

H

C-C

H

CH

, I

a

M. 2

37.4

-242

" 27

5 a

7 H

H

H

O

H

CH

,CH

,CH

3 C

H,

Ia

M

. 217

.6-2

20.8

" 27

5 a

TA

BL

E 5

. 3

,4-S

tero

ido

-Py

razo

les

(con

t.)

__

-~

_

__

__

-

Met

hods

of

R""

' sy

nth

esis

M

.p.

or

B.p

. R

efer

ence

s D

criv

ativ

es

* N.

R'

R"

R"#

R'"

w

rp

~_

__

__

_

._

8 H

H

H

O

H

C-C

CH

3 C

H,

Ia

D

ec. -143"

275

a

9 H

H

C

H,

OH

C

H,

CH

, I

a

M. 156-174"(d)

275

a

10

CH

, C

H,

H

OH

C

H,

CH

, I

a

M. 269.2-274.6"

275

a

Met

ho

ds

of

N.

R

R'

R"

R"'

sy

nth

esis

M

.p.o

r B

.p.

Ref

eren

ces

Der

ivat

ives

1 O

H

H

H

H

Ia

M

. 272-276.6"

275

a

N, 0

-dip

rop

ion

yl

deri

v.:

M. 107.6-112.6"

2 O

H

CH

,CH

, H

H

I

a

M. 284.4-290.6"

275

a

3 O

H

CH

=CH

, H

H

I

a

M. 247-259.4"

275

a

4 O

H

C=

CH

H

H

I

a

M. 239.6-246.2" 275

a

5 O

H

CH

,CH

=C

H,H

H

l

a

M. 239.8-248.2"

275

a

6 O

H

H

OH

H

I

a

M. 233.2-246"

275

a N

, O(R

)-D

ipro

pion

yl d

eriv

.: M

. 107.6-112.8"

7 O

H

CH

, 4-

Ia

M

. 233.2-246.8"

275

a

Met

hods

of

N.

R

R'

syn

thes

is

M.p

. or

B.p

. R

efer

ence

s D

eriv

ativ

es

1 O

H

H

Ia

M

. 231

-233

.6"

275

a

2 O

CH

, H

I

a

M. 2

36.4

-239

.2'

275

a

3 O

H

CH

, I

a

M. 2

70.4

-276

" 27

5 a

~-

~

Met

hods

of

N.

R

R'

syn

thes

is

M.p

. or

B.p

. R

efer

ence

s D

eriv

ativ

es

1 O

H

H

Ia

M

. 272

.8-2

77"

275

a A

w

U

l

2 O

H

CH

,CH

, I

a

M. 3

05-3

15"

275

a

rl

D? u

L-

L?

0 @a w rl I

rl * rl

i

W f-

5: 5:

n B v) rl

W r3

i i

P Q

2 2

I

m

u D? u

N m

436

I!-

I:

I: I

W

4 p* rl I c) p* 3

z!

0 W d. 3 I

N p* 3

i .. a U cd k

iz

a, +.'

ii: k

.. a, c, d

V

ii: E; ?

Q, r(

0 3

CO- 3 0 3

c- 0 ln

0 Ln cu

W

5 Ln

3 r(

W 3 I-I

I

a

Ln c- 3

0 3

W r3

W W cu

z! ai m P

in

u m

u G u 2 u 2 u

/ I x Y-0 in

2 u I I m

In =W

=W u kz u 3 u

2 3 u

2 3 u 2 u 2 u

r( Q) 5 r(

437

m W c- W

& Q) I t- Q)

s .. a, Y cd

V

ii

w- w i w- + r w m t - O N N N Q )

3- In- w- t-- m m - t - w N m m 3

m N N N m W

2 2 od m

N 3 I

m

N 3 c-'

a

V

P V d ,

3 8 v n a

m N w

m > 2 3 I

3 t- 3

m'

El 3

2 u

< u

N 3

m N *

El 3

W w m

3 W 3

s

P

El

w 0 m W x 3 N

m 0

2 k 3 3

m 3

m ' d

El 7 w rd

Y U

El 3

P I

% u k7 u - Q (D t- w 3 3 3

v c- N

0 f- c-

- 3 3

N 0 c3

0 N

I u3 3

i% m l-l

a i a i

d d U U

d U

n =a V V

It m V

n

=a V

N N

El P

2" 4 j n =W u

n 0

xW V

?.a V

n n =W V

=W V

v N

W cu u3

N l-l N

0 N

43 9

m W m

co rl m

i

P

fi

Y)

=a + n

=&I

u

0 m

In c- c-

h -8 I

N w

i

P

fi

?TJ e

n

5 u

N m

co W n

0 rl t-

2

P

fi

0 8 10 =.

u

m n

In m N

b W N I 0 c- N

n

0

d ii

Ern u

x"

Q w m

0 t- t-

a a * d

44 1

TABLE I. 1, 3 ( o r 5)-Alkyl- o r Aryl -d isubs t i tu ted P y r a z o l e s (with unass igned s t r u c t u r e )

~~ ~~

Methods of N. R R' s y n t h e s i s M.p. o r B.p. R e f e r e n c e s D e r i v a t i v e s

1 CH,OH CH3 IV a M. 79" 500

IV a M. 183" 5 6

H?C B r

3 - CHZ +OH CH, IV a M. 206' 56

CH3 B r

C 6 H 5 CH,CH,COOH 111 b o r d M. 120" 1049 Ag salt

B. 235"/20

CH2CH(OCH3), VI a M. 94.5" 343 &NO2

CH(CH,), I a 249

C6H5

C6H5 -+ I a M. 127" 146

C 6 H 5 M. 90-91" 150

442

m 0 3

c W 3

I

i

4 :: f

0 * 3 3

3 1 1

443

I I

3 3

3 0

I (D 0

- 3

m

m 0

m 3 - 3 - 3 3

* l n D ( D t - o m 3

444

20

CH

,CH

,NH

, C

6H

5

21

CH

,CH

,N(C

H,)

, C

6H

5

VII

I

Na

519

B. 133-135"/1

205,519

B. 125-128"/1

205

.2H

C1:

M. 1

82-1

85"

.HC

I: M. 135-136"

.2H

C1:

M. 18

5-187"

B. 1

68

-17

1"/

1

519

.HC

k M

. 216

-218

'

VII

I M. 63

-64"

519

B. 200-202°/1

.HC

1: M

. 198-200"

23

CH

,CH

,NH

CH

2C6H

,

24

CH

,CH

=CH

, C

H3

111

d

Na

M

B. 171"

51

51

51,65

Pic

rate

: M

. 77.5-18.5"

25

CH

2C,H

, C

H3

Id

Illd

IV a

VII

I

B. 141.5"/15

55,72

B. 13

7"/10

72

55,72

519

Pic

rate

: M

. 114"

.HC

L M. -105"(d)

26

CH

,C,H

,

27

CH

,C,H

,

CH

,C1

CH

,OH

V

IU

B. 150-153"/ 12

519

28

CH

,C6H

,

29

CH

,C,H

,

CH

,OC

,H,

CH

,CO

OH

VIU

VII

I

B. 160-165°/15

519

M. 125-127"

519

Eth

yl e

ster

82%:

B. 158"/12

Met

hyl

amid

e 90%:

M. 70

-71"

Nit

rile

30

CH

,C,H

,

.a

Ir

01

31

CH

,C,H

,

CH

,CH

,NH

, V

III

CH

,CH

,NH

CH

, V

Ill

519

519

.2H

C1:

M. 183-185"

Dip

icra

te: M. 136-138"

.2H

C1:

M. 146-148"

TA

BL

E 8

. (co

nt)

. ~

P

a

0)

N.

R

32

CH

,C,H

,

38

CsH

5

39

CsH

5

R'

CH

,OH

CC

l,

~~

-_

M

eth

ods

of

syn

thes

is

M p

or

B p

R

efer

ence

s _~

_

__

~~

-

--

-

-

IIf

M. 5

8-60

" 48

9

VI

a 46

3

VI

a M

.11

8-1

18

.8"

97

0

VI

a-IV

a

589

IV a-VI

a 58

9

IV a

-VI

a 58

9

Ia

B

. 250

-260

" 2

38

,27

1,2

72

,37

6,1

14

0

d

B. 2

54-2

55"

/753

5

5,7

2,7

84

,81

4

III

c B

. 132

-133

"/1

6 1

19

,12

0,1

04

6

d

B. 1

23'/1

2 3

,26

5,2

72

c,d

B

.140

"/7

22

6

In c

-VII

I 10

46

Vb

3

5,5

45

,56

4,5

65

,66

4,6

65

,97

5,9

76

,97

7

C

678

e 66

5

a, b

3

5,5

37

,97

7

VI

a 4

40

,10

83

IIf

489

Id

M

. 85-

86"

88

1

Der

ivat

ives

~~

~~~

~~

- -~

~~

Dip

icra

te:

M. 1

66-1

68"

Pic

rate

: M

. 113

-114

"

Hyd

razo

ne:

M. 1

60-1

61"

Hyd

razo

ne:

M.

126-

127"

Hyd

razo

ne:

M. 1

06"

.HC

1

.HC

L

ptC

lq:

M. 1

733d

d)

Pic

rate

: M

. 72-

73'

W

m W m r

0 n m N C m h3 N m m 3

LD N 0 N

(D

I I LD 3

3

N Ln

3 * d, +

Ln

0; m

m 2 3 c

i i i i

447

Po 3

t- t - 0 m m * c- c *

W o * - i n c 3 m F

Ln 3 3

448

0 Lo 3

L O N 3 N"

c 0 0 0 3 N - N t- m m 3 - 3 m L o m m m c u3

Q $ I m U 9

Lo

N m m (c, m W

m

N 3 3

3 I 3 m 3 :

i m

'C 5 P I 5 5

c 3

3 r- : : I

d LO W r- (0 W a N W w w 0 3 w w m

LO c m L D L D

449

e w P - w o w w m c o

0 N

0 m 4

I W

2

2 a

m m 3 4 4 4 w w m m

0 m W I

m

icj cd

%

W P - w

450

9 C

H,C

,H,

10

C

H,C

,H,

11

CH

,C,H

,

12

CH

,C,H

,

13

CH

,C,H

,

14

CH

,C,H

5

15

C

,H,

16

C,H

,

* ul w

CH

,OH

V

III

B. 1

46-1

48"

/0.2

51

5

CH

20C

2H5

VII

I B

. 11

5-11

7"/0

.1

515

CH

,CH

,NH

2 V

III

B.

110-

140"

/0.1

51

5

CH

,CH

,NH

CO

OH

V

III

515

CH

,CO

OH

V

III

/NH

2 4

H,C

H

VII

I 'C

OO

H

CH

3 I

a

d

I11

b

IX

*

CH

2CI

IV b

515

M.

243-

244"

51

5

M.

43"

847

B.

264-

266"

20

2

B.

134-

135"

/16

16

9

B.

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rate

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Pic

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d d 3 u

r" V m z

LD

XW V

r" V 51

LD

z? V

m N t- N

m N

0 3 m m

m N 0 3

co 3

rd 3

N W m n

X m X X

W m ln m * W

X 0

t- m 0 * m a ,

m m

5 5 1

m

(D *

m m m m m m

m

m m m m m m

N v) 3

3 In 3

I

r:

3:

co *

w m w m c o m

X 3 1 3 :

0 3 v ) L n m *

5 5 3

TA

BL

E 2

3b.

Py

razo

le-1

-Car

boxy

lic

Aci

ds w

ith

Una

ssig

ned

Str

uctu

re, a

nd t

hei

r F

unct

iona

l D

eriv

ativ

es

N.

R

R'

R"

Met

hods

of

X

synt

hesi

s M

.p.

or

B.p

. R

efer

ence

s D

eriv

ativ

es

5 C

H,

H

6 C

H,

H

7 C

H,

H

8 C

H,

H

9 C

H,

H

H

CO

NH

,

H

CO

NH

,

H

CO

NH

,

H

CO

NH

,

CH

,CH

,CH

, C

ON

H,

C(C

H,)

, C

ON

H,

CH

,CH

,CH

=C(C

H,)

, C

ON

H,

'CiH

5 YH

M. 9

3"

Ia

M

. 90

"

Ia

M

. 78

-79"

XX

Vf

M.

148"

Ia

M

. 95

"

M.

113-

114"

Ia

M

. 88-

89'

Ia

318

751,

752

751,

752

452

191

318

603

320

.HN

O,:

M.

185"

CO

NH

, I

a

M. 1

69-1

7Oo(

d) 1

054

d 10

54

W W w

cd n

m

cd U

0 3 rl rl

W W *

t- 0 Q)

W W w

rd n

r. m U

+g 0

cd U

m

% u

m

d U

F3 rl

LL? u

cd H

N

m 2 8

ri m 3 0 I

m m u

555

TA

BL

E 23b.

(con

t.)

cn

cn

OJ

N.

R

R'

Met

hod

s of

R

"

X

syn

thes

is

M.p

. or

B.p

. R

efer

ence

s D

eriv

ativ

es

M. 1

33-1

34"

10

25

16

H

(CH

,),C

H

CH

, C

Hy

CO

NH

, I

a

\/ \

/

C -

CH

-CH

/

\

17

CH

,

18

CH

3 -C

HZ

CH

,C=C

H-

I CH

,CH

,

19

CH

, -C

(CH

,),C

H,C

=CH

--

I CH

,

CO

NH

,

CO

NH

,

CO

NH

2

Ia

Ia

Ia

M. 1

20"

43

3,43

4

M. 1

65"

Id)

174

M. 1

24"

91

9

20

CH

,CH

, -C

HzC

HZ

CH

ZC

Hz-

C

ON

H,

Ia

M

. 126

-127

"

173

21

C6H

, - C

H2C

HZ

CH

2CH

z-

CO

NH

, I

a

M. 1

64"

13

4

CO

NH

C,H

, X

XV

f M

. 115

-116

"

134

TA

BL

E 2

4.

N-U

nsu

bst

itu

ted

Py

razo

le-3

(o

r 5

)-C

arh

ox

yli

c A

cid

s an

d t

hei

r F

un

ctio

nal

Der

ivat

ives

.

N.

R

R'

X

Met

ho

ds

of

syn

thes

is

M.

p. o

r B

. p.

R

efer

ence

s D

eriv

ativ

es

1H

H

C

OO

H

CO

OC

H,

CO

OC

,H,

CO

N(C

H,C

H,

),

CO

NH

CH

,CH

,N(C

,H,)

,

- C

ON

HC

H,C

H,N

CO

NH

NH

,

Va

VI

a-I1

1 d

VI

a-V

III

XV

II a

XX

V h

I1 a

I1 c

I1 a

VII

I

VI

a

VII

I

VII

I

VII

I

VII

I VII

I

VII

I

M.

210-

212"

M.

215"

M.

141"

M.

16

0

M.

67,

5-68

"

M.

147-

149"

M.

159-

160"

M.

70"

M.

120-

121"

M.

175"

M.

166-

168"

506

Ag

-sal

t

217

Cu

-sal

t

59,

75,

76,

519,

82

9

21

3,4

05

,54

8,8

92

,89

4,1

08

8

506

863

461,

504

863,

864

78

0

59

518

78

0,1

13

5

78

0

367

36

7

561,

864

a

Pic

rate

: M

. 16

5"

Dip

icra

te:

M.

182"

m m N

0 0

O d N t - N i

I / m o i t - N 3

$ 2

5 5

2 r u 0 0 0 0 v v

s

c

N

e m i I

m m i

s

0 (D t- m a +

TA

BL

E 2

4. (

co

d)

UI

Met

hod

s of

m

0

N.

R

R'

x sy

nth

esis

M

. p.

or

B.

p.

Ref

eren

ces

Der

ivat

ives

I a

-Ill

a

XV

II a

CO

OC

H,

CO

OC

,H,

la

VII

I

CO

NH

, V

III

CO

N(C

H,

), V

III

CO

N(C

,HS

),

VII

I

CO

N(C

H,C

H,C

H,)

, V

IIl

0

/C*,

C%

\

'.cH,cH

,/ C

ON

,

CO

NH

C,H

, V

IlI

CO

NH

NH

, V

III

CO

NH

N=

CH

C,H

, V

III

-CO

NH

h-l

H

(I> Or113

V

III

CO

NH

N=

CH

C'H

=C

HC

,H,

VII

I

CO

NH

N-C

(CH

, ),

VII

I

/CH

3 V

III

-CO

NH

N-C

-CO

NH

N=

CH

V

III

I I I 1

H - C

--O

H

HO

- C

-- H

H-C

-OH

CH

,OH

M.

75-7

8"

M.

82-8

3"

M.

178-

179"

M.

136-

137"

M.

151-

152"

M.

162"

M.

183"

M.

153-

154"

M.

237-

239"

M.

258-

260"

M.

258"

M.

23

9

M.

217"

M.

188-

189"

0"

10,4

99,6

27,

629,

893

, 98

8

60

326,

548,

1088

778

76

6,7

80

78

0

78

0

78

0

3 59

766

32

6,7

78

778

778

778

778

778

778

Dia

cety

l d

er:

M.

173-

174"

a m c - m t - t -

t- m * N N 3 +

L- ii m o w w m 0 0 m o w m m w w m 3 - 3 m a m

w w - d g l v m m W N m m m i 3 L - m t - c - t - m m

m e V

X

- i m m z

t- 4 m w , - I +

m m 0 4 3 N

X

4 N

X

N ea

561

TA

BL

E 2

4. (

cant

.)

vl

Met

ho

ds

of

m

N N.

R

R'

X

syn

thes

is

M. p

. o

r B

. p.

R

efer

ence

s D

eriv

ativ

es

-

23

H

24

H

25

H

26

H

27

H

28

H

C6

H5

C

OO

H

9

OH

CO

OC

H,

CO

OC

,H,

CO

NH

NH

,

C O

OC

,H ,

CO

NH

NH

,

la

la

f

VII

I

XV

II a

Ib

I1 a

Ia

I1 a

V

III

Ia

If

\'I11

VII

I

Ia

If

VII

I

M.

198-

199"

M.

231-

232"

M.

235-

237"

M. 26

2"

M. 17

7-17

8"

M. 1

81-1

82"

M. 14

0"

M.

205"

M.

123-

124"

M. 31

0-36

5"(d

)

M.

222"

M. 1

33.

5"

M.

275"

M.

215"

M.

281"

457

247,

550

,

30

1

78,2

16,2

27

771,

955,

988

320

520

216

78,2

27

216,

535

22

1

92 5

925

925

846

846

302

302

36

9

Cu

-sal

t: M

. 32

0"

Hy

dra

zin

e sa

lt

CO

OC

,H,

Ia

M

. 19

1"

36

9

29

H

.H

,O:

M.

219"

. C

OO

H

CO

OC

,H,

CO

NH

NH

,

VIII

Ia

M

. 13

2-13

4"

I a-

VII

I M

. 19

5-19

6"

775

17

5

715

30

H

C

OO

H

CO

OC

,H,

VII

I M

. 25

0"

Ia

M.

162"

31

H

I

a-V

III

M.

235"

C

ON

HN

H,

QfH

3 C

ON

HN

H,

H3C

C

OO

CZ

H5

I

I a-

VII

I M

. 23

9"(d

) 3

92

32

H

33

H

CO

OH

CO

OC

,H,

CO

NH

NH

,

XV

II a

M

. 30

8-31

0"(d

)

VII

I M

. 17

0"

VII

I M

. 26

0"

43

1

275

215

Pic

rate

: M

. 24

2-24

5"

a

CO

OH

X

VII

a

M. 3

28"

364

34

H

35

CH

, C

H3

CO

OH

CO

OC

H,

VII

I M

. 21

6-21

1"

VI

a M

. 14

0-14

2"

XX

VII

I

I1 a

M

. 14

5. 5

"

60

60

25 a

154,

755

01

8

36

CH

,OH

37

C

H,

CH

,OH

C

OO

C ,H

5

VII

I M

. 26

5-26

1"

CH

,CO

OH

C

OO

H

198

TA

BL

E 2

4. (

con

t.)

cn

m

N.

R

R'

X

Met

hod

s of

sy

nth

esis

M

. p. o

r B

. p

. R

efer

ence

s D

eriv

ativ

es

,@

38

CH

, -c

HaC

,C

H,C

H2

CO

OH

"

>O

CO

OC

2H,

\CH

,CH

,

39

CH

, 'G

HS

CO

OH

CO

OC

, H,

CH

,CH

3 C

OO

H

C O

OC

,H

40

CH

,CH

3

41

CH

,CH

,CH

3 C

H3

42

C,H

, C

H,

43

C,H

,

44

CG

H,

CH

,CH

3

CG

H,

CO

OH

CO

OC

,H,

CO

OH

CO

OC

H,

CO

OC

,H,

CO

OH

CO

OC

,H,

CO

OH

VIII

M. 235-236"

VII

I

VI a-VIII

M. 234-236"(d)

VIII

M. 248-250"

la

M. 102-103"

VII

I M. 194"

11 c

B. 135-140"/5

VIII

M. 245"

I1 c

B

. 142-144"/3

VIII

M. 265"

Xa

M. 154"

XXVIII

I1 c

M

. 12

2"

B. 165-173"/3

VII

I M. 241"

I1 c

M

. 127-128"

B. 155-165"/3

111

a

M. 261"

198

198

59

59

205

817

817

817

817

498

25 a

817

817

817

29

.HC

l: M

. 160-161"

N t- N

2

m 4 N

565

w w w m m m

w w m m

in

5 8 8 m u

u u

i m N m

m m w w

4 3 8 u u

m W

w t- N

z'

m m

566

CO

OC

,H,

Ia

M

. 11

0-11

1"

B.

20

8-2

10

"/1

4

63

56

-CH

(CH

~)C

H~

CH

(CH

,)C

H~

- C

OO

H

CO

OC

H,

CO

OC

,H,

57

Q

-H2C

59

CO

OH

CO

OC

,H,

CO

OH

CO

OC

,H,

CO

OH

CO

OC

H,

VII

I M

. 26

9-27

0"

VII

I M

. 9

0-9

1"

B.

197"

/12

Ia

B

. 19

7"/1

2

VII

I M

. 31

0"(d

)

Ia

M

. 1

73

-17

4"

I a-

I11

a

Ia

M

. 25

5-25

8"

I a-

111

a M

. 26

1-26

2"

I a-

I11

a M. 9

1 -9

2"

111

c-X

a-

-VIl

I

VII

I M

. 29

8"

111

c-X

a

Xa

M. v

ery high

la

M. 27

3-27

4"(d

)

63

63

63

89

9

89

9

605

998

997,

998

998

30

30

30

30

275

a

.HC

1: M

. 15

6"

TA

BL

E 2

5.

Pyr

azol

e-3-

Car

box

ylic

A

cid

s an

d th

eir

Fu

nct

ion

al D

eriv

ativ

es

N.

R

Met

hod

s of

R

' R

" X

sy

nth

esis

M

. p.

or

B.

p.

Ref

eren

ces

Der

ivat

ives

1 C

H,

H

H

CO

OC

H,

2 C

H,C

,H,

H

H

CO

OC

,H,

3 C

6H5

H

H

CO

OH

CO

OC

H,

CO

OC

,H,

CO

NH

NH

,

CO

N,

CN

H

H

H

H

CO

OH

CO

OH

IV a

B

. 12

0"/9

54

IV a

M

. 75-

76"

519

B.

150-

160"

/0.6

I11

d

M.

143-

146"

VI

a-X

VII

a

VII

I

XV

II a

I1 f

M

. 72"

VII

I M

. 17

"

111

d

VII

I

VII

I M

. 13

8"

VII

I M

. 74

"(d)

I1 f

272

36

,96

2

881,

963

35,

119,

272

48

9

27

2,8

81

,96

3

963

347

347

347

488

XV

II a

M

. 19

3"

77

0

VII

I M

. 231

"

311

6 C

H,

C6

H5

C6

H5

10

C

6H,

11

-1

12

C6H

,

13

CH

,

H

C6

H5

H

CH

, H

CH

,CH

, H

CH

,(C

H,)

,CH

, H

CH

,(C

H,)

,CH

, H

'BH

S

H

H

CH

3

CO

OH

Co

cl

CO

OC

H,

CO

NH

,

CO

NH

C 6

H5

CO

OH

CO

OC

H,

CO

OC

2H5

CO

OH

CO

OH

CO

OC

,H,

CO

OH

CO

OC

,H,

CO

OH

CO

OC

,H,

CO

OH

CO

OC

,H,

CO

OH

CO

Cl

CO

OC

H,

IV a

VII

I

IV a

VII

I

VII

I

IV a

XV

II a

VII

I

VII

b

VII

I

VII

b

VII

I

VII

b

VII

I

Ia

Ia

IV a

VII

I

VII

I

IV a

M. 171"

M.

73 -7

4"

M.

37-3

8"

M.

158-

160"

M.

94"

M.

132"

M.

122-

123"

M. 1

70"

M.

129"

M.

69"

M.

119"

M.

46"

B.

220"

/2

M. 1

19"

M. 55

"

M.

227-

228"

M. 1

76-1

78"

M. 6

0"

B,

120-

125"

/13

60,

884

Ag

Sal

t

887

60

887

887

95

95

95

16

9

416

416

416

416

416

416

808

808

884

312,

884

71

887

.H,O

. M

. -1

00"

M. 71

.5-7

2.5"

71

,312

.C

H,I:

M. 17

2"

W 02

i e

5

j h:l I I m

m i

t- i

570

0 m

I m t-

2

w m 3

m m X X

0 N 3 N N N m

N

5 7 1

H

H

TA

BL

E 2

5. (

cont

.)

Met

hod

s of

N.

R

R'

R"

X

syn

thes

is

M. p

. o

r B

. p.

R

efer

ence

s D

eriv

ativ

es

CO

OC

,H,

la

77

0

24

0.

H.

-

CO

OH

VIII

M.

160-

180"

7

70

25

CO

OH

la

M.

216-

217"

35

5, 6

02,

96

9

VI b

M. 2

29-2

31"

527

VIII

355,

527

, 96

9

XVII a

M. 1

22-1

24"

548

CO

OC

H,

Ia

M.

174-

175"

52

7,77

0

M.

182-

183"

CO

OC

,H,

I a

M.

78-7

9"

96

9

WV a

M. 9

6-9

7"

355

28

ON

02

29

e2

do,

30

O

N0

2

902

31

O

H.

H

CH

3 C

OO

H

Ia

M

. 239

-241

" 60

2

CH

,CH

3 C

OO

C,H

, I

a

M.

91"

533

CH

,CH

3 C

OO

H

Ia

M. 19

3"

533

M.

181"

53

3 C

H,(

CH

,),C

H,

cOO

C,H

, I

a

CH

,(C

H,)

,CH

, C

OO

H

Ia

M

. 15

0"

533

CO

OC

,H,

Ia

M. 1

65"

533

CO

OH

V

III

M.

290-

292"

7

70

m m

2

0 c- t-

m

N m

2

rd I

X

N m

m m 0 - m m m m m

W

m m W W m m

m W m m m iD N W w

qq" m U m

l l

m m v)

m m W

W W W 3 ,+

2 2

rd I

in

EN

8 0 V

X 8 u I1 u U

I I

rd c(

in 8 V

$ V

51 V

v-v

I

I1 Ll?

x X 31 X m m X m

m m 0 m m -r

t- m

-F m W m m m

m m

5 1 3

m cc Ln

0 i 3

i

rb - =N

8 0 V

e

4 A,,

Y i l 1--3

m

in

% V

N d

m

m d

d m m d m 00 d m 00 v m m

m a 3: e 0 0 V

8 V

8 V

8 V

51 3: 9 3: m

c-4 LC i Ln 0 m m d

m m m Ln v m

5 7 5

TA

BL

E 2

5. (

con

t.)

01

Met

hod

s of

N.

R

R'

R"

X

syn

thes

is

M.p

. or

B.p

. R

efer

ence

s D

eriv

ativ

es

4

56

C,H

,

57

C,H

,

58

C,H

,

*,H, C

OO

H

VII

I -

H

CO

OC

,H,

Ia

HJa: C

OO

C,H

, I

a

CO

OH

V

III

H

CO

OH

V

III

CO

OC

,H,

Ia

H

59

C

,H,

n C

OO

H

VII

I

CO

OC

,H,

Ia

C O

OH

V

III

CO

OC

,H,

I a

61

C

,H,

H

c H3

CO

OC

,H,

Ia

CO

OC

,H,

VII

I C

H3

M. 20

8"

M.

126"

M.

195"

M. 8

1"

M. 2

15"

M.

168"

M. 1

66"

M. 98

"

M.

253"

M. 1

15

-11

7"

M. 2

18"

M. 1

51"

M.

15

7-1

59

"

36

9

36

9

912

Ag

salt

912

37,

912

37

77

5

77

5

77

5

775

36

8

36

8

10

76

10

76

W P- O 3

3

(D 3

I 0 W 3

2

z? V

21

(0 c- 0 d

(D c- 0 d

W c- 0 3 d

t- 3 d P- 3

m 2 0 N

I I 0 0 N

I

3

c- 3

0 c- 1

0) 3

v m 1

2 2 2

rd

2 x

X

3:

0

4 LJ

Xrn V

Ern u

m 0 W P-

m W P- W 9 u3 W

W (D 10

TA

BL

E 2

5. (

cont

.)

cn 4

mN

R

M

eth

od

s of

R

' R

" X

sy

nth

esis

M

.p. o

r B

.p.

72

CH

,

73

CH

,

74

CH

,

75

C

H,

76

CH

,

77

CH

,

78

CH

,CH

,

79

CH

,CH

,

--C

H,C

H,C

H,-

-cH

,CH

(CH

,)C

H,-

-CH

,CH

,CH

,CH

, -

-CH

,CH

,CH

,CH

(CH

, 1 -

-CH

,CH

(CH

~)C

H,C

H, -

- C

H2C

H,C

H, -

-CH

,CH

,CH

,CH

,

CO

OH

CO

OC

H,

CO

OC

,H,

CO

OH

CO

OC

H,

CO

OC

,H,

CO

OH

CO

OC

H,

CO

OC

,H,

CO

OH

CO

OC

H,

CO

OH

CO

OC

H,

CO

OH

CO

OC

H,

CO

OH

CO

OC

H,

CO

OH

VII

I

VII

I

Ia

VII

I

VII

I

Ia

VII

I

IV a

VIl

I

Ia

IV a

-VII

I

VII

I

I a-

VII

I

IV a

-VII

I

VII

I

IV a

-VII

I

VII

I

VII

I

1V a

IV a

-VII

I

M.

208"

(d)

M.

96.

5-97

"

M.

175-

175.

5"

B.

i3n

-i4

0a/

iz

M.

208.

5"

M.

87-8

8"

B.

194"

/12

M.

170.

5"

B.

18

5-i

87

~/i

i

M.

114-

115"

M.

176-

177"

M.

73 -7

4"

Ref

eren

ces

Der

ivat

ives

86

86

86

86

86

63,

97

63

,97

63,

97

63.

97

63

63

63

63

63

63

63

63

63

63

CO

OC

H,

VII

I M. 1

08-1

09"

63

--C

H~

CH

,CH

~C

H(C

H,)

- C

OO

H

CO

OC

H,

CH

,CH

(CH

,)C

H,C

H,

-

CO

OH

CO

OC

H,

IV a

-VII

I

VII

I

M.

127.

5-1

28.

5"

B.

182-

183"

/10

63

63

80

CH

,CH

,

81

C

H,C

H,

82

CH

,CH

,

.H,O

: M

. -9

4"

IV a

-VII

I

VII

I

M. 1

47.5

-149

. 5"

M. 44

. 5-

45.

5"

63

63

CH

(CH

,)C

H,C

H(C

H,)

CH

, -

CO

OH

CO

OC

H,

M.

141-

141.

5"

M.

64.5

-65.

5"

B.

188-

189"

/11

63

63

IV a

-VII

I

VII

I

83

CH

,C,H

,

84

CH

,C,H

,

85

C

H,C

,H,

86

CH

2C,H

,

-CH

,CH

,CB

,CH

, ~

CO

OH

CO

OC

H,

M.

157.

5-1

58.

5"

M.

69-7

0"

63

63

IV a

-VII

I

VII

I

-CH

,CH

,CH

,CH

(CH

,)

-

CO

OH

CO

OC

H,

-CH

~C

H(C

H,)

CH

,CH

, -

CO

OH

CO

OC

H,

-CH

(CH

,)C

H,C

H(C

H,)

CH

, ~

CO

OH

CO

OC

H,

IV a

-VII

I

VII

I

63

63

.H,O

: M

. 11

9-12

1"

B.

242-

246"

/11

M. 1

43.

5"

M.

98-9

9"

IV a

-VII

I

VII

I

63

63

IV a

-VII

I

VII

I

M.

137-

138"

M.

112-

113"

B.

242-

243"

/11

63

63

86,4

16

86

86

416

87

C,H

,

01 4

W

-CH

ZC

HZ

CH

2-

CO

OH

CO

OC

H,

CO

OC

2H,

VII

I

VII

I

Ia

VII

b

M. 2

16.

5"

M. 14

0. 5

"

M.

143"

M. 2

20"

CO

OH

V

III

416

TA

BL

E 2

5. (

con

t.)

En

m 0

N.

R

R'

R"

X

CO

OC

,H,

89

C

,H,

- C

H2C

H,C

H,C

H2 -

CO

OH

90

91

C,H

,

92

C,H

,

93

C,H

,

94

C,H

,

CO

OC

H,

CO

OC

2H,

CO

OH

CO

OC

2H,

CO

OH

CO

OC

H,

CO

OH

CO

OC

H,

CO

OC

,H,

-CH

(CH

,jC

H,C

H(C

H,)

CH

, -

CO

OH

CO

OC

H,

-CH

2CH

2CH

2CH

,CH

2 -

-CH

2CH

2CH

,CH

2CH

, -

CO

DH

CO

OC

2H,

CO

OH

CO

OC

,H,

Met

hod

s of

sy

nth

esis

M

.p. o

r B

.p.

Ref

eren

ces

Der

iva

tiv

es

VII

b

M.

119"

41

6

Ia

M

. 16

3-16

4"

48,

97

VII

I 41

6

VII

I M

. 10

9-11

0"

48

VII

b

M.

99"

416

VII

I M

. 221

" 41

6

VII

b

M.

138"

41

6

I a-

VII

I M

. 17

7-17

8"

63

VII

I B

. 23

8-24

0"/1

2 6

3

VII

I M

. 19

6.5-

198.

5"

6

3

VII

I M

. 11

9-12

0"

63

Ia

M

. 128

-129

"

63

I a-

VII

I M

. 19

3. 5

" 63

VII

I M

. 87

-88"

63

B.

240"

/11

VII

I M

. 16

2"

VII

b

M. 9

5"

VII

I M

. 205

"

VII

b

416

416

416

116

( D L D

b V 3 3

a m a 0 0 m m m 0 0 m m m m m

m m a m m m m m m m m m

m m m m P J,

58 1

cn

N

m

N.

R

R'

R"

TA

BL

E 2

6.

Pyr

azol

e-3

(or

5)-C

arb

oxyl

ic A

cid

s (w

ith

Un

assi

gned

Str

uct

ure

) an

d t

hei

r F

un

ctio

nal

Der

iva

tiv

es

-

1 C

H=C

HC

OO

CH

, H

C6

H5

C6

H5

5 C

6H5

6 C

6H5

C6

H5

H

H

H

H

H

H

H

CH

,CH

,

CH

,CH

,

CH

,CH

,CO

OH

CH

,CH

,CO

OC

,H,

CH

,CH

,CH

,CH

,

CH

,CH

,CH

,CH

,

X

CO

OC

H,

CO

OH

CO

OC

,H,

CO

OH

CO

OC

,H5

CO

OH

C O

OC

, H

CO

OH

CO

OC

,H

CO

OH

CO

OC

,H5

CO

OH

CO

OC

,H5

Met

hod

s of

sy

nth

esis

M

. p.

or

B. p

. R

efer

ence

s D

eriv

ati

ves

I1 a

-IV

a

IV a

VII

I

Ia

VII

I

la

VII

I

Ia

VII

I

Ia

VII

I

Ia

Ia

Ia

M.

110-

110.

5"

M.

135-

136"

B.

125-

127"

/3

M.

140-

141"

B.

152-

154"

M. 1

65-1

67"

M.

83-8

4"

M.

13

7-1

39

M.

59-6

0"

Dec

. 18

5"

M. 2

04"

M.

186-

87"

863

863

1001

1001

1001

1001

1043

, 104

9

10

43

,10

49

241

241

601

601

601

601

Na

salt

m m m m N N N m m m m r(

ro 0 3

2

I

P

i ln N

I 0 v) N

- m m N

u' B

X

m N i d 3 0

i

583

TA

BL

E 2

la.

Pyr

azol

e-4-

Car

box

ylic

A

cid

s an

d t

hei

r F

un

ctio

nal

Der

iva

tiv

es

N.

R

R'

X

Met

hod

s of

R

" sy

nth

esis

1H

H

2 C

H,

H

3

CH

2C6H

, H

H

CO

OH

H

CO

OC

H,

CO

OC

,H5

CO

OH

H

CO

OH

H

CO

OC

,H,

CN

CO

OH

CO

OC

H,

CO

OC

,H,

H

111

a b, d

Va

c6

YV

II a

VII

I

la

VIl

l

V c

6

XV

II a

VII

I

VII

I

V c

6

III

d b, d

VII

I

XV

II a

II f

la

VI

a b

M. p

. or

B.

p.

M. 2

70-2

75"

M.

278-

279"

M.

76-7

8"

B.

120-

130"

/0.6

M. 2

05-2

06"

M.

208-

209"

(d)

M.

151-

152"

M. 6

2-63

"

M.

63-6

4"

M.

214-

215"

M.

221-

222"

M.

128-

129"

M.

96-9

7"

M.

99-1

00"

Ref

eren

ces

__ -

20

8,2

09

211,

548

, 55

2

515

506

278,

515

515

518

515

506

383,

506

515

515

515

266

57

2,6

35

1045

115,

11

6,3

80

,94

9

1045

, 1

04

6,1

04

7

48

8,4

89

35

3,8

09

1111

1046

10

45

,10

46

,10

47

Der

iva

tiv

es

Ag

salt

10

H

cn

m

UI

'tjH

5

CN

CO

OC

,H,

COOH

COOCZHS

CN

C O

OH

COOC,H,

CN

CN

COOH

CO

OC

,H,

C ONHC fi H

,

CO

N11

<>C

H, 01

H5

COOH

C-H

, COOC,H,

CONHC,H,

H

H

H

H

VI

a

VlI

I

Vl

b

XV

II a

vi a

Vi

a

VII

I

XV

II a

VI

a

VIl

l

Vi a

VII

i

VI

a-vm

I

a

VII

I

la

13

Ia

VIE

I1 a

Id

Ia

M.

95"

M.

133-

134"

M.

253-

254"

M.

161-

162"

M. 1

62-1

63"

M.

250"

.

M.

183-

184"

M.

190-

191"

M.

174-

175"

M.

228Y

d)

M. 54

"

M.

179"

M.

179"

M.

163"

M.

260"

12

,11

10

383,

797

1046

1047

3 84

12

12

12

12

1111

12

12

,11

10

12.1

110

59, 7

5, 7

6, 8

30

307

.H,O M

. 46

"

165

.HC

L M

. 16

0"

307

307

307

308

M.

111.

5-11

2.5"

96

M.

85-8

6"

308

M.

182"

30

8

HCI: M. 20

0"(d

)

* F

rom

met

hyl (01. et

hyl)

fo

rmy

l-ac

etat

e ph

enyl

(o

r p.

brn

mop

heny

lj-h

ydra

zone

by

low

-pre

ssu

re d

isti

llat

ion

x

!Y

586

s, m s m m a

m 3 1 O W f 2 - 3 3 m 3

c d

6 0

W E q q a .c

$6 4

C

fix ;- 31

c N

iD t - m N N N

587

W 0 0 W 0 Fa

0 0 t- e 3

r.2 2

V 3

V -

3 z 0 0

I I

d id

588

32

C6

HS

H

35

CH

3 C

H3

36

CH

3 C

H3

37

CH

, c6

11S

38

CH

zOH

C

6H

5

- @a 39

C,H

, C

H3

(D

0C21

l5

CN

CN

CO

OH

CO

OH

CO

OH

CO

Cl

CW

*H

S

Id

M. 165"

306

Id

M. 118"

309

Id

M. 182"

459

Id

M. 212"

459

I11 b

M. 248"

41 1

C

6H

S

CH

II

I b

M

. 199-200"

235

CH

VIII

V c6

XVIl a

VIU

CO

NH

,

CO

NH

C6H

,

CO

OH

C

6H

5

CO

OH

C

H3

CO

OC

H,

CO

OC

,H,

CH

3

CO

OH

C

H3

la

IV a

VII

I

VII

I

M. 217"

887

506

450

887

887

M. 37"

887

M. 200'

887

M. 15

9"

887

M. 61-68"

B. 140-150'712

IV a

M. 176-177'

884

Ia

M. 197-198"

884

IV a

884

IV a

-VII

I M. 63

-64"

884

IV a

M. 110-112"

913

Anhydride: M. 143"

VIII

M. 194-196"

145, 546,869,979,1024

Ag

sa

lt

XVII a

M. 200-201"

385,450

K s

alt

Anhydride: M

. 189.5"

885

x

L

p:

i

590

49

C,H

, C

H,O

C,H

,

50

C

,H,

CH

,

53

C,H

, C

H,

54

C,H

, C

H,

54

CO

OH

CO

OH

CO

OC

H,

CO

OH

CO

OH

CO

OH

CO

Cl

CO

OC

*H

,

CO

NH

CN

CO

OH

CO

OC

ZH

S

CH

3

CH

,CO

CH

,

CO

OC

<CH

', 'C

H-

Id

VII

I

VII

I

la

I a-

VII

I

I a-

VII

I

VIE

XV

ll a

VlI

I

la

d

VI

a

VU

I

VIU

Ia

d

VII

I

VII

l

Ia

VIU

M

178'

M

17

8-1

79

'

M

125

M. 1

58"

M.

88"

M.

18

5"

M. 2

05'

M. 78

. 6-

80.

1"

M. 19

3-19

4.

5"

M. 1

89

"

M.

218"

M.

225"

(d)

M.

146"

M.

146'

148

143

143

14

3,9

78

183

183

141,

562,

567,

10

86

385

824

14

1.

562,

567

, 10

85

824,

971

, 11

25

80

129

82

4

239,

759

824

824

569,

803

567,

569

,727

569

Ag

sa

lt

Oxi

me:

M.

20

9-2

11

"

Ph

enyl

hyd

razo

ne:

M

222'

Ph

enyl

hyd

razo

ne:

M. 2

65-2

66'

Ag

salt

: M

. 22

2'

K s

alt

Ag

salt

TA

BL

E 2

7a.

(con

t.)

Ln

m

X

N.

R

R'

R"

56

C6H

5

57

C,H

,

58

C6

HS

59

C,H

s

60

C,H

,

61

C

,H,

62

C,H

,

63

C,H

,

64

C6

H5

Q

--('a

s

CO

OH

CO

OH

CO

OC

,Hs

CO

OH

CO

OC

,H,

CO

OC

,H,

CO

OH

CO

OC

,Hs

CO

OH

Met

hod

s of

sy

nth

esis

VIl

l

VlI

I

VII

I

VII

I

la

VII

I

VU

I

VII

I

VII

I

VIU

la

VlI

I

M. p.

or

B. p

R

efer

ence

s D

eriv

ati

ves

M. 2

61

"

M. 2

08-2

10"

M.

158-

160"

M.

236"

(d)

M.

121-

122'

M.

244"

M.

18

6"

M.

155-

156"

M.

157.

5"

M.

202"

M.

210"

M.

128"

M.

251"

M.

261"

569

129

12

9

12

9

12

9

12

9

12

9

129

12

9

569

567,

569

,727

387,

567

, 56

9

Su

lfon

e: M

. 16

2"

m W rn m m -

t - c t- m m m m

m (0

m m

0 0 s. m U U

in

3 9 U B LD W t- a w W

EW 3 t- m a a

A

m o a t -

593

TA

BL

E 2

7a. (

can

t.)

01

u? R

' X

R

"

N.

R

CO

OH

CO

OC

,H,

73

C

,H,

CO

OH

c-

2H5

I4

C,H

, 's

H5

CN

CO

OH

CO

W 2%

15

C

,H,

<J-

g O

-CH

Z

76

C

,H,

C6

H5

C

ON

H ,

CN

77

C,H

, C

6H

5

78

C

,H,

CG

H5

CN

CO

OH

CO

OC

H,

CO

OC

,H,

CO

NH

____

M

eth

ods

of

syn

thes

is

VlU

XI

a

__

_._

VII

I

XI

a

v1n

XI

a

Ia

VII

I

XI

a

VII

a

VLU

VII

I a

VII

I

XV

lI

Xa

11 e

VII

a

XI

a b

Ie

V

III

M. p

. or

B. p

. R

efer

ence

s D

eriv

ati

ves

M.

17

7-1

78

"

M

88

-89

"

M.

207-

208"

M. 1

05.5

-106

.5"

M.

210"

(d)

M.

10

7-1

08

"

M.

15

8"

M.2

04

"(d

)

M. 9

7-9

8"

M. 21

1"

M. 1

63

-16

4"

M.

205"

(d)

M. 2

38-2

39"

M.

14

0-1

41

"

M.

145-

146.

5'

M. 1

99-2

00"

73

1

73

1

121,

72

9

72

1,1

29

72

7,7

29

721,

72

9

148

73

1

73

1

418

418

418

148

30

4,4

98

,72

8,9

45

385

498

482

41

1

12

8

75

8

304

418

6

9 U

8 8

m N t-

m -r 3

t- W 3

i

z V

4

N a m

595

TA

BL

E 2

7a.

(con

t.)

yl

(D

R'

01

N.

R'

X

Met

hod

s of

D

eriv

ati

ves

R

"

syn

thes

is

M.p

. or

8.p

. R

efer

ence

s

85

C,H

, I

a

M. 81

-02

" 89

7 C

OO

C',H

, C

"3

CO

OH

C

H:,

V

III

M. 20

3'(d

) 7

31

CO

OC

,H,

XI a

M. 94

-95

' 731

B

L

6 k 0

m * Ln W t-

597

Y 3

rd

P

d, a

d,

1

k

x

e:

i l

x x 5: x x

x x &? x x u

N P ?

598

CO

OC

H,

IV a

CO

OC

,H,

Ia

d

CO

NH

, V

III

/CH

, --

c,H

2 -C

O-N

P

' CH

, -C

H,

B.

91"/

11

71,3

12

72

72

887

M.

165"

M. 7

5-76

"

3 59

7 C

H,

H

M. 1

83-1

84"

78

49

,95

95

CO

OH

IV

a

CO

OC

H,

IV a

CO

OC

,H,

IV a

8 C

H,

9 C

H,

H

H

CO

OC

,H,

IV a

M

: 93

O

369

CO

OC

H,

IV a

CO

OC

,H,

IV a

M.

79-8

1"

775

M.

60"

775

10

C

H,

CO

OC

H,

IV a

M

. 11

4"

368

H

H

11

CH

,CH

, C

H3

CO

OH

in

11

CO

OC

,H5

IV a

M.

141-

142"

71

B. 1

01.

5"/1

2 71

P

icra

te:

M. 6

8-69

"

M.

162-

163"

78

B.

193-

194"

/12

78

12

CH

,CH

, C

6H

5

H

CO

OH

V

III

CO

OC

,H,

IV a

H

CO

OH

CO

Cl

CO

OC

zH

M.

140-

141"

35

9

B. 8

9"/1

1 35

9

B.

128-

141"

/23

359

TA

BL

E 2

8.(

con

t.)

m

0

N.

R

0

Met

hod

s of

sy

nth

esis

M

. p.

or

B.

p.

Ref

eren

ces

Der

iva

tiv

es

R'

R"

X

,CH

, --

C,H

, -C

O-N

/o

\c

H,-

-cH

, M

. 85

"

359

H

CO

OH

CO

Cl

CO

OC

,H,

,CH

, - C

,H2

-CO

-N

/o

\CH

,-

CH

,

VII

I

IV a

M.

124"

B.

101-

102"

/11

B.

122"

/11

51

3 59

51

14

CH

,CH

=CH

, C

H3

M. 7

9-80

"

359

M.

99-1

00"

M.

87-8

8"

M.

156"

CO

OH

X

VII

a

988

CO

OH

X

VII

a

988

72

988

72

CO

OH

V

III

XV

II a

IV

a

C O

OC

, H ,

B.

170-

171"

/9

M.

117-

118"

M.

189-

190"

18

C

H,C

,H,

19

C

,H,

H

H

988

CO

OH

X

VII

a

CO

OH

I

a

d

Xd

XV

II a

XX

V b

VlI

I

26

4,2

72

,96

9 A

g sa

lt

72

3,2

64

,26

5

988

962

888

CO

Cl

M.

39-4

1"

B.

160-

164"

/17

N t- N N N w t - r : N

0 r- t- m m W

W co 3 N r- -r

- m a (00 - F a N C U

3 m m

m m I ": 4

0 0

t- 3 N

i

W W

I m W

2

m t- N

2

rd rm rd

a a m m m z

x Y

W N v) cu 3 N 0 N w N m

N N N

601

w 3 m

N N N

I 3 N N

2

rd 3

m : 8 V

51

u,

V X V

I 1

V

c-. N

* m m

0 - 6 o m m w m w m m

t - t -

0 N

X

Xrn V

XW V

m m 3

c- m 3

2

3

s P-

X

V 8

B V

r " r " v v Xm V V

m m o N @ a m

B

m r,

3 N m m

34

C

H,

CH

, C

OO

CH

, M. 1

74-1

75"

20

0

VII

I

35

C

6H5

36

C

,H5

CO

OH

X

XV

III

25 a

M. 20

1-20

2"

M. 1

38-1

40"

CO

OH

CO

OC

,H,

XX

VII

I

XX

VII

I

25 a

25 a

37

C,H

5

38

C

H,

CO

OH

X

XV

III

M. 22

2"

25 a

-CH

,CH

,CH

, C

OO

H

CO

OC

H,

CO

OC

,H5

VII

I

VII

I

Ia

M. 20

0. 5

"

Oil

86

86

86

M. 2

07-2

08"

B.

158-

160"

/14

39

C

H,

CO

OH

CO

OC

H,

Ia

IV a

63,

97

63,

97

CH

,CH

,CH

(CH

, )C

H, -

40

C

H,

CO

OH

I

a-V

III

IV a

-VII

I

M. 1

95-1

95.

5"

63

63

41

CH

,

42

CH

,

43

CH

,CH

,

44

CH

,CH

,

0)

g

45

CH

,CH

,

46

CH

,CH

,

-CH

(CH

, )C

H,C

H,C

H,

--

-CH

,CH

(CH

, )C

H,C

H(C

H,)

-

-CH

,CH

,CH

, ~

-

-CH

,CH

,CH

,CH

, -

-CH

,CH

,CH

(CH

,)C

H,

-

-CH

(CH

3)C

H,C

H,C

H2

-

CO

OH

CO

OH

CO

OH

CO

OH

IV a

-VII

I M. 1

28-1

30"

M. 1

79-1

80"

M. 1

78-1

79"

M. 1

48-1

49"

63

IV a

-VII

I 63

IV a

-VII

I 86

IV a

-VII

I 63

CO

OH

IV

a-V

III

M. 1

84-1

85"

M. 4

3-49

"

63

CO

OH

IV

a-V

III

63

TA

BL

E 2

8.(c

ont.

)

m

,D

N.

0

R

R'

R"

X

41

48

49

50

51

52

53

54

55

56

-CH

,CH

(CH

~)C

H,C

H(C

H,)

-

-CH

2CH

2CH

,CH

, -

-CH

2CH

2CH

(CH

3)C

H, -

-CH

(CH

, )C

H2C

H2C

H, -

-CH

,CH

(CH

, )C

H,C

H(C

H,)

~

-CH

2CH

2CH

2 -

-CH

,CH

2CH

2CH

2 -

-CH

,CH

,CH

(CH

,)C

H,

-

-CH

(CH

, )C

H,C

H,C

H, -

-CH

,CH

(CH

,)C

H,C

H(C

H,)

-

CO

OH

CO

OH

CO

OH

CO

OH

CO

OH

CO

OH

CO

OH

CO

OH

CO

OH

CO

OH

Met

ho

ds

of

syn

thes

is

IV a

-VII

I

IV a

-VII

I

IV a

-VII

I

IV a

-VII

I

IV a

-VII

I

I a-VIII

I a-

VII

I

I a-

VII

I

I a-

VII

I

I a-VIII

~

M.

p. o

r B

. p.

R

efer

ence

s D

eriv

ativ

es

M.

145-

146.

5"

M.

187-

187.

5"

M.

186-

187"

M.

154-

154.

5"

M.

15

9.5

-16

0.

5"

M.

217.

5"

M.

194-

195"

M.

202-

203"

M.

180-

181"

M.

223"

63

63

63

63

63

86

48,

97

63

63

63

TA

BL

E 29a.

Py

razo

le-1

, 3-D

icar

box

ylic

Aci

ds

and

th

eir

Fu

nct

ion

al D

eriv

ati

ves

.

N.

R

R'

Met

hod

s of

X

x'

sy

nth

esis

M

. p.

or

B. p

. R

efer

ence

s D

eriv

ativ

es

1H

C

H3

CO

OC

,H,

CO

NH

,

CO

NH

C,H

,

CO

OC

,H,

CO

OC

,H,

CO

NH

,

2H

C

H,C

H,

CO

NH

,

CO

NH

,

3H

C

H,C

H,C

H,

CO

NH

,

4H

C

H,C

H(C

H,)

, C

ON

H,

CO

NH

,

5H

C

H,(

CH

,),C

H,

CO

NH

,

CO

OH

la

CO

OH

I

a

CO

OH

xx

v f

CO

OC

H,

XX

Vf

CO

OC

,H,

CO

OC

,H,

Ia

CO

OH

la

CO

OC

,H,

Ia

CO

OH

I

a

CO

OH

I

a

CO

OC

,H,

CO

OC

,H,

Ia

M. 174-175"

Dec

. 155"

M. 232-234"

M. 158-160"

M. 82"

B. 178-179"/13

M. 131"(d)

M. 167"

M. 112-113"

M. 165-166"

M. 123"

M. 58-59"

60

600

470

60

67

60

53 2

532

532

53 2

532

532

TA

BL

E 2

9a.

(con

t.)

Met

hod

s of

N

. R

R

' X

X'

syn

thes

is

M.p

. or

B.p

. R

efer

ence

s D

eriv

ati

ves

m

m

0

6 7 8 9 10

11

12

CH

,(C

H,)

,CH

,

CH

,(C

H,

),cH

,

CH

, (C

H, )

,cH

,

H

H

CH

3

-CH

,CH

,CH

,CH

,

CO

OH

CO

NH

,

CO

NH

,

CO

OH

CO

NH

,

CO

NH

,

CO

OH

CO

NH

,

CO

OC

, H,

CO

OC

, H

CO

OC

H,

CO

NH

C,H

,

CO

OC

,H,

CO

OC

, H,

CO

OC

,H,

CO

OC

,H

CO

OH

CO

OH

CO

OC

,H,

C O

OH

CO

OH

CO

OC

,H,

CO

OH

CO

OC

,H,

CO

OH

CO

OC

H,

CO

OC

,H,

CO

OC

,H,

CO

OH

CO

OC

H,

CO

OH

CO

OC

, H ,

VII

I

la

la

VII

I

Ia

la

VII

I

Ia

xxv

f

xxv

f

xxv

f

xxv

f

Ia

xxv

f

M. 167"

M.

161-

162"

M.

61-6

3"

M. 1

56"

M.

145-

148'

M.

55-5

6"

M.

139-

141"

M. 6

5-67

"

M.

156-

157'

M. 8

6-87

"

B.

177"

/13

M. 1

5-7

6"

M. 1

05-1

06"

M.

148.

5-1

49.

5"

M. 8

4. 5

-86"

B.

185"

/10

M.

158.

5-1

59.

5"

M.

92-9

3.

5"

53 2

53 2

532

532

532

53 2

532

532

60

60

93

93

58,6

0

97

97

97

TA

BL

E 2

9b.

Py

raz

ole

-l,3

(o

r 5

)-D

icar

bo

xy

lic

Aci

ds

(wit

h u

nas

sig

ned

str

uc

ture

) an

d th

eir

Fu

nct

ion

al D

eriv

ativ

es.

N.

R

R'

X

Met

ho

ds

of

X'

syn

thes

is

M.p

. o

r B

.p.

Ref

eren

ces

Der

ivat

ives

1

H

CH

,(C

H,)

,CH

, C

ON

H,

CO

OH

I

a-V

III

Dec

. 80

-82"

60

1

M.

160-

163"

18

8

2 H

C

H=C

(CH

,),

CO

NH

C6H

5 C

OO

C,H

, I

a

M. 2

38-2

39"

3

H

C6H5

CO

OC

H,

CO

OH

X

XV

f M

. 126

-126

.5"

54

CO

OC

H,

CO

OC

H,

XX

Vf

M.

95"

54

CO

OC

,H5

CO

OC

,H,

M.

80-8

1"

67

TA

BL

E 3

0.

Py

razo

le-1

, 5

-Dic

arb

ox

yli

c A

cid

s an

d th

eir

Fu

nct

ion

al D

eriv

ativ

es

~~~~

Met

hods

of

N.

R

R'

X

X'

syn

thes

is

M.p

.or

B.p

. R

efer

ence

s D

eriv

ativ

es

1

C6H

, C

,H,

CO

OC

H,

CO

OC

H,

Xa

M

. 150

" 29

N N N

s 0" s: 2

a

2 zm m V

3 N m

608

TA

BL

E 3

1a.

Pyr

azol

e-1,

4-D

icar

box

ylic

Aci

ds

and

thei

r F

un

ctio

nal

Der

ivat

ives

.

TA

BL

E 3

2.

Pyr

azol

e-3,

5-D

icar

box

ylic

Aci

ds

and

thei

r F

un

ctio

nal

Der

ivat

ives

~~~

~ ~

-

~~

-----

Met

hod

s 01

N

R

R'

X

X'

syn

thes

is

M p

or

B.p

. R

efer

ence

s D

eriv

ativ

es

1H

H

C

OO

H

CO

OH

xv

n a

M 2

90"

(d )

457,

548

,629

N

a sa

lt

__

_

__

_

__

- - -~

63

1,7

62

,89

3

K s

alt

99

3,1

08

8

Ag

salt

Ca

sal

t

2H

CO

Cl

CO

OC

H,

CO

Cl

CO

OC

H,

/CH

,-\H

, ,C

H,-

-I;F

I,

SO

N

p

=ON,

,O

k

H,

- C

H,

CH

,-C

H,

CO

N,

CO

N 3

CH

, C

OO

H

CO

OH

CO

OC

H,

CO

OC

H,

CO

OC

ZH

5 C

OO

C2H

,

CO

OC

,H,

CO

OC

H,C

OO

H

3H

C

H,C

OO

H

CO

OH

C

OO

H

.m 0

"4

H

CH

,CO

OC

H,

CO

OC

H,

CO

OC

,H,

* F

rom

eth

yl a

-ace

tace

tyl-

hyd

razo

ne

of

tetr

ahyd

rofu

ran

-(%

, 3,4

)-tr

ion

e by

hea

tin

g w

ith

HC

1 30

%.

Ba

salt

M. 3

10

359,

1101

.A

nhyd

ride

:

M. 8

6-87

"

359,

1101

VI

a

M.1

51

.5"

21

7

894

b

M. 1

53"

21

7,8

04

,89

3

VII

I M

. 184

" 35

9,11

01

M. 1

94-1

96"

Dec

. 120

-122

"

561

VI

a-V

III

M. 3

13"

59

Ag

sali

vm

M. 3

15"

37

2,5

04

,10

57

XV

II a

38

9, 5

39, 5

40,

1057

I1 c

M

. 128

-129

"

804

I1 a

M

. 10

6-10

7"

3 72

* M

. 18

1"

1057

VII

I M

. 23

4-23

5"(d

.)

278

I1 a

M

. 109

-110

"

278

TA

BL

E 3

2. (

cont

.)

N.

n R

' X

X'

Met

hod

s of

sy

nth

esis

M

.p. o

r B

.p.

Ref

eren

ces

Der

iva

tiv

es

5H

c6

rf5

CO

OH

C

OO

H

I1 a

-VII

I

I1 c

-VII

I

Vl

a

VlI

I

XV

II a

VI

a

VI

a b

XV

II a

IV a

-VII

I

Dec

. 243

-246

"

94

,20

8,2

12

, 552

20

8,2

12

, 552

210

215

389

215

20

9,2

10

221

506

61

359,

1101

359,

1101

359.

1101

CO

OC

H,

CO

OC

,H,

CO

OC

,H,

CO

OC

,H,

M.

104-

105"

M.

96"

6 C

H3

7 C

H,C

H,

H

H

CO

OH

CO

OC

H,

CO

OH

CO

Cl

CO

OC

,H,

M. 250"(d.)

M. 7

2-73

.5"

M. 24

3"

B.

125"

/12

CO

OH

CO

OC

H,

CO

OH

CO

Cl

CO

OC

,H,

/CH

,-C

H,

--C

ON

)O

\C

H,-

CH

, C

H,-C

\H,

CH

,-C

H,

-CO

P(

p

VII

I M

. 12

3"

359.

1101

8 C

H(C

H,)

, C

OO

H

CO

Cl

CO

OC

H,

CO

N(C

H,)

,

M. 2

85"

B.

145-

146"

/17

M.

66"

M. 1

04-1

05"

359,

1101

359,

1101

359,

1101

359,

1101

H

VII

I

M.9

9.5

"

359,

1101

M. 1

47"

35

9,11

01

X m X X X

3 - 0 3 m 3 N 1 - 3

611

TA

BL

E 3

2 (c

ontd

.)

01 -

N.

R

R'

X

X'

Met

hods

of

syn

thes

is

M.p

. or

B.p

. R

efer

ence

s D

eriv

ativ

es

CO

OC

,H,

/CH

,-C

Hz

-CO

N

;o \C

H,-C

H,

/CH

,-C

H,

-CO

N

>o

\CH

,-CH

,

CO

OH

CO

Cl ,C

HZ

--C

HZ

-C

ON

,O \*

\CH

,-CH

,

CO

OC

,H,

CO

OC

,H,

/CH

z-C

H,

CO

N

>o

\CH

,-C

H,

359

359

M.

79"

15

C

H,C

,H,

H

16

C

H,C

H,C

,H,

H

M. 13

9-14

0"

M. 22

4"

M. 8

6"

M. 1

10"

359,

1101

CO

OH

CO

Cl

359

359

359

$2

CH

,-C

H,

17

C

H,C

OC

,H,

H

18

C

,H,

H

CO

OC

,H,

/CH

z-C

H,

-CO

N

>o

\CH

,-C

H,

CO

OH

M. 12

8"

359

359

CH

,-<

H2

CH

,-C

H,

-co<

p

CO

OH

X

VII

a

M. 2

66"(

d.)

112,

246

, 21

2, NHJ s

alt:

M.

210"

53

2

10

01

A

g sa

lt 96

3 C

a s

alt

Pb s

alt

963

246,

272

272

M. 2

70-2

72"

Vm

CO

OC

H,

CO

OC

H,

CO

NH

,

CO

OH

CO

OC

H,,

CO

NH

,

XV

II a

M

. 164

"

vn1

M. 1

27-1

28"

VIl

I M

. 190

"

H

CO

OH

C

OO

H

M. 2

56-2

51"

XV

II a

31

2

20

CH

,CH

,CH

(CH

,),

CH

, C

OO

H

CO

Cl

CO

OH

CO

Cl

M.

223"

B.

176"

/16

359

359

N N d N

6 1 3

TA

BL

E 3

3a.

N-U

nsu

bst

itu

ted

Py

razo

le-4

, 5

(or

3)-D

icar

box

ylic

Aci

ds

and

th

eir

Fu

nct

ion

al D

eriv

ati

ves

Met

hod

s N

. R

X

X

' of

sy

nth

esis

M

.p.o

r l3

.p.

Ref

eren

ces

Der

iva

tiv

es

1H

C

OO

H

CO

OH

V

a-V

III

VI

a-V

III

VI

a-X

VII

a

XV

II a

* C

OO

CH

, C

OO

CH

, I1

a

VI

a b

Va

CO

OH

C

OO

C,H

,

CO

OC

,H,

CO

OC

,H,

Id

CO

OC

,H,

CO

NH

, V

III

CO

NH

, C

ON

H,

VII

I

CO

NH

C,H

, C

ON

HC

,H,

M. 2

44"

M. 2

60"

M. 1

41"

M. 2

63"

(d.)

M. 6

9-70

"

B. 1

80-1

85"

/2

B. 1

60-1

65"

/0.5

M. 2

48-2

50"

M. 3

27"

(d.)

M. 2

44"

863

832

243,

827

278,

635

, 408

, 83

2

1084

a

863

832

76

863

522

522

522

36

6,1

08

4

409

2 C

H,

3 C

H,O

CH

,

4 C

H,C

H,

5 C

H,C

H,C

H,

C6

H5

CO

NH

NH

, C

ON

HN

H,

VII

I

CO

OH

C

OO

H

VI

a-V

III

X a

-VII

I

CO

OC

H,

CO

OC

H,

11 a

CO

OC

H,

CO

OC

H,

IIa

CO

OC

H,

CO

OC

H,

I1 a

CO

OC

H,

CO

OC

H,

I1 a

CO

OH

C

OO

H

I1 a

-VII

I

-CH

ZC

HZ

CO

OC

H,

CO

OC

H,

CO

OC

H,

9

I H

XV

II a

I1 a

VII

I

I1 a

M.

>300

" 5

17

M. 2

29-2

30"

59

332

M.

106"

86

3

B. 1

54-1

56"/

0.00

01

863

B.

150-

152"

/0.0

5 86

3

B.

140"

/0.

005

863

M.

235"

(d.)

94,2

08,2

12,

K s

alt

552,

955

955

M.

179-

181"

86

3

Dee

. 260

" 86

3

M. 1

99"

863

* Fro

m p

yraz

ole,

K,C

O,

and

CO

, at

50

atm

., by

hea

ting

at

260"

in

pre

sen

ce o

f C

dF,

0 7-l

OY W co

d Y Y

m W 00

rd U U

m

1 r3

N r3

D W a

J

2

r"

0 (0 m

t- 4 f

0

E d d

TA

BL

E 34. Pyrazole-3,4-Dicarboxylic A

cid

s an

d t

hei

r F

un

ctio

nal

Der

iva

tiv

es

N.

R

R'

X X'

Met

hod

s of

sy

nth

esis

M

.p. or

B.p

.

H

H

CO

OC

H,

CO

OH

CO

OC

H,

CH

3 C

OO

H

CH

,

CO

OC

H,

CO

OH

or

CO

OC

,H5

CO

OC

,H,

CO

OH

CO

OC

,H,

CO

OH

CO

OH

CO

OC

,H,

CO

OC

H,

I1 f

CO

OC

H,

I1 f

CO

OH

X

VII

a

VII

I

CO

OH

V

III

XIV

a

XV

II a

CO

OC

H,

I1 f

CO

OC

,H,

or

CO

OH

X

IV a

-VIE

CO

OC

,H,

VII

a

VII

I

XIV

a

CO

OH

CO

OC

,H,

CO

OH

CO

OH

C-

A

VII

I

XVII a

VII

a

VII

I

VII

I

XIV

a

XtV

a-V

III

M.234"

M. 89"

M. 97-98"

M. 247"

M. 185"

M. 51.5"

M. 265" (d

.)

M. 276"

(d.)

M. 264" (

d.)

M.158"

Ref

eren

ces

Der

iva

tiv

es

489

118,120,169

489

118

234,425

NH

: salt

226,234,982

Ag

salt

226,572,982

489

982

425

234,982

226,234,982

411

412

411

230

230

230

230

b I t-

5: I

:: N

I /

m

620

d

N LD m a m - o - N N N x N N 2 t- N * W

6 2 1

TABLE 3

4. (

can

t.)

0)

Met

hods

of

N.

R

R'

X

X'

syn

thes

is

M.p

. or

B p

. R

efer

ence

s D

eriv

ativ

es

29 0 0

CH

, C

OO

H

CO

OH

V

lll

M. 2

87"

(d.)

2

30

CO

OH

C

OO

H

VII

I M

. 285

" (d

.)

23

0

CO

OC

,H,

CO

OC

,H,

XIV

a

M.

168"

2

30

N

30

00 NHCO

CH

3 C

H,

32

H

5C

ZO

OC

~C

OO

CI

H~

HzC

,

33

a

CH

,

CH

,

CH

,

CO

OH

CO

OC

,H,

CO

OH

CO

OC

zH5

CO

OH

CO

OC

,H,

CO

OH

CO

OC

,H,

VII

I

XIV

a

VII

I

XIV

a

M. 30

2" (d.)

M. 1

41"

M. 25

0"

M. 82

"

23

0

23

0

23

5

23

5

c 6

%

CO

OC

,H,

CW

,H

,

VIl

a

M. 1

72"

16

7

35

C

OO

CH

, C

OO

CH

, X

a

M.1

36'

30

K s

alt

Ag

salt

TA

BL

E 35.

Pyrazole-4,5-Dicarboxylic

Aci

ds an

d th

eir

Fu

nct

ion

al D

eriv

ativ

es

m

N

w

N.

R

R'

X

1

CH

,

2 C

H,C

H,

3 C

,H,

'6'5

H

H

H

CH

,

CO

OH

CO

OH

CO

Cl

CO

OC

H,

,CH

,-CH

, -C

ON

' P

\C

H,-

CH

,

CO

OH

CO

OC

H,

CO

OC

H,

or

CO

NH

,

CO

OC

,H,

CO

NH

,

CO

NH

C ,H

5

CO

OH

CO

OH

CN

CO

OH

CO

OC

,H,

CN

CO

OC

,H,

CN

X'

CO

OH

CO

OH

Co

cl

CG

QC

H,

,CH

,--

C,H

2 <O

N,

,O

CH

,-CH

,

CO

OH

CO

OC

H,

CO

NH

, o

r C

OO

CH

,

CO

OC

,H,

CO

NH

,

CO

NH

C &I5

CO

OH

CN

CO

OH

CO

NH

NH

C,H

,

CN

CO

NH

C,H

,

CO

NH

NH

C 6

H5

CO

NH

NH

C,H

,

Met

ho

ds

of

syn

thes

is

XV

II a

~-

XV

II a

vm

VII

I

Id

VII

l

VlI

l

VII

I

XV

II a

VII

I

VII

I

VII

I

If

Ia

Id

I a-

VII

I

M.p

.or

B.p

. _

__

__

B.

204-

207c

'/20

M.

84"

M.

215-

216"

(d

.)

M.7

5-76

"

M.

186"

B.

168-

173"

/0.7

M. 25

3-55

" (d

.)

M.2

05-2

06"

M.1

98

-19

9"

M.

202-

203"

M.

250-

251"

M. 2

12"

(d.)

M.2

53"

M.8

8-89

"

M.1

67-1

68"

M.

147"

M. 2

07"

Ref

eren

ces

Der

ivat

ives

506

.2H

,O:

M.

233-

35

9

.H,O

: M

. 1

79

-

35

9

359

3 5"

180"

35

9

12

0,2

66

,63

5

Ag

Sal

t

12

0,2

66

B

a sa

lt

266

522

266

266

15

3,1

55

14

2,1

43

,22

6,

572,

982

15

5

Ag

sal

t

15

3

15

3,1

52

15

5

15

3

15

2,1

53

15

3,1

56

TA

BL

E 3

5. (

con

t.)

m

N

P

N.

R

R'

X

X'

Mct

hod

s of

syn

thes

is

M.p

. or

B.p

. R

efer

encc

s D

eriv

ati

ves

CN

CO

OC

H,

CO

NH

,

CN

CN

CO

OH

CO

OH

CO

OC

H:,

CO

NH

NH

C 6

H5

CO

N H

NH

C

CO

OH

CO

NH

NH

C 6

H5

CO

NH

NH

C,H

,

VII

I

XV

II a

VII

I

VII

I

vm

I a-

VII

I

VII

I

1 a-

VII

I

VII

I

I a-

VII

I

M.

190"

M. 1

97"

(d.)

M.2

17"

(d.)

M. 1

50

.5-1

51

.5"

M. 2

69"

M.

21

5-2

16

"

M. 2

08

-20

9"

M. 2

66-2

68"

M. 2

24

-22

5"

15

6

Ba s

alt

567

15

6

80

15

6

15

6

15

6

15

6

15

6

15

6

TABLE 36a.

Pyrazole-3,4,5-Tricarboxylic A

cid

s an

d t

he

ir F

un

ctio

nal

Der

ivat

ives

.n

N

UI

~-

N.

R X

X

' x

Met

ho

ds

of

syn

thes

is

M .p

. or

B .p

. R

efer

ence

s D

eriv

ativ

es

in

C

OO

H

coon

co

on

VII

I M

.213

" 2

06

,21

1,2

14

, A

g sa

lt

XV

II a

M

. 233

" 2

78

,89

1,8

94

, N

a sa

lt

297

10

57

cooc

n,

CO

OC

,H,

cooc

n,

cmc,

n,

CO

OC

H,

CO

OC

,H,

I1 a

C

Vll

l

Id

I1 a

VI

a

CO

NH

, C

ON

H,

CO

NH

, V

III

coN

nc,n

, co

ivnc

6n5

coN

nc,

W,

VII

I

CO

NH

NH

, c

oN

nN

n,

CO

NH

NH

, V

lIl

co

Nn

N.

cn

c,N

, c

oN

nN

-cn

c,n

, c

om

N=

cn

c 6n

5 V

III

-CO

NH

N

-co

Nn

N

-c

om

N

VII

l I1

II II

nc

cH

-cn

c,n

, n

cc

H-c

nc

,n,

nccn

=cnc

,n,

M.1

18

"

M.

91"

K s

alt

Hy

dra

zin

e

salt

: M. > 325"(d.)

21 1

21 1

21 1

516

.2n

,0:

M.

71-

297

214

2 97

M. >

270"

2

91

M. >

300"

29

7

297

297

297

TA

BL

E 3

6a.

(con

t.)

Met

hods

of

01

N

m N.

R X

X

' X

"

syn

thes

is

M.p

. or

B.p

. R

efer

ence

s D

eriv

ativ

es

CO

N,

CO

N,

- C

ON

HN

HC

O-

- C

ON

HN

HC

O-

-CO

NH

NH

CO

-

--C

ON

HN

HC

O-

-CO

NH

NH

CO

-

- co

oco

-

2 C

H,C

H,C

H

(CH

,)P

C

OO

H

CO

OH

CO

OC

H,

CO

OC

H,

,CH

,-C

H,

,CH

,-C

H,

-CO

N

>O

-CO

N,

>O

k

H,-

CH

, C

H,-

CH

,

C6

H5

C

OO

H

CO

OH

CO

OC

,H,

CO

OC

,H,

-C>W

CO

OH

C

OO

H

CO

OC

,H,

CO

OC

,H,

CO

N,

CO

OH

CO

NH

C b€

i5

CO

NH

NH

,

CO

NH

N-C

HC

,H,

CO

N,

CO

OC

H,

CW

H

CO

OC

H,

,CH

,--C

H,

CH

,-C

H,

-CO

N\

>o

C W

H

CO

OC

,H,

CO

OH

CO

OC

,H,

VII

I

v I11

VIl

I

VII

I

VII

I

VII

I

VlU

VII

I

VII

I

XV

II a

Id

VII

I

XV

II a

VII

a

M.7

0"

B. 2

02"

/30

M. 1

77"

M.4

7"

M. 1

45"

M.

184"

M

213-

214"

M.7

4-7

4.5

"

M. 2

05"

(d.)

M. 7

6"

297

297

297

297

2 97

2 97

297

20

6,2

1 I

359

359

359

522

Ba

salt

22

6,5

72

,98

2

522

m,

o:

~.7

0-7

30

41

1

411

41

1

rn a,

cd > k

.2 Y

.rl

a" ill a, c) c a, k a, W

2

4

4

Q k 0

E

W

orn rn '-

2 % 3 5 5 5

X

k

X

e:

d 627

0,

N

m

TA

BL

E 3

7.

Dip

yraz

olyl

carb

oxyl

ie A

cid

s an

d t

hei

r F

un

ctio

nal

Der

iva

t,v

es

N.

R

R'

R"

RI

Met

hod

s of

R;

R;

syn

thes

is

1H

H

C

H,

H

H

CO

OH

2H

H

C

OO

H

H

H

CO

OH

3H

C

OO

CH

, C

OO

CH

, H

C

CO

CH

, C

OO

CH

,

4H

H

C

H,

CH

, C

H,

CO

OH

5H

C

H,

CO

OH

C

,H,

H

C,H

5

C6

H5

H

H

6

H5

H

C

OO

H

I C

,H5

H

C6

H5

C

H,

CH

, C

OO

H

CO

OC

H,

XV

II a

XV

II a

11 a

la

VI

a

XV

Il a

1 a-

VII

I

VU

I

VI

a

M.p

.or

B.p

.

M.

325"

(d

.)

M. 2

95'

(d.)

M. 1

70"

M. 2

47-2

48"

M.

273.

5-27

4"

M. 2

25-2

6"

(d.)

M.

256-

256.

5"

M.1

28-1

29"

Ref

eren

ces

Der

iva

tiv

es

4 24

4 24

86

3

200

200

962

200

200

200

Ref

eren

ces

Der

iva

tiv

es

Met

hod

s of

N.

R

R'

R

R,

R;

R;

syn

thes

is

M.p

.or

B.p

.

1 /C

OO

CH

, /C

OO

CH

, -C

C

OO

CH

, C

OO

CH

, -C

C

OO

CH

, C

OO

CH

, II

a

M. 2

20"

86

3

\CH

.CO

OC

H,

"CH

GW

CH

,

z

d 0

u,

4

r 0 0 U

d U

d

- 630

d c d

E # cd E

m

63 1

TA

BL

E 3

8. (c

ont.

)

0)

w

Met

hod

s of

N.

R

It'

R"

R"'

sy

nth

esis

M

.p. o

r B

.p.

Ref

eren

ces

Der

iva

tiv

es

H

CO

OH

X

VII

a

M. 2

60-2

61"

499,

502

C6

H5

6

H5

CO

OC

H,

TI a

2

9

C6

H5

-

0B

r

H

CO

OC

H,

Ha

M

. 95"

50

2

7 -@

G

Br

H

C

OO

CH

, I1

a

M.

106-

108"

50

2

8 e

.3

eO

CH

3

H

CO

OC

H,

II

a

M. 9

2"

502

H

CO

OC

H,

II

a

M. 9

1" (

d.)

30

lo 0 0

C6

H5

C

OO

CH

, I1

a

M. 1

41"

(d.)

3

0

9 00

11

C6H

5 g

H5

C

OO

CH

, C

OO

CH

, I1

a

M. 9

3"

29

A

12

C

6H5

VC

H,

CO

OC

H,

CO

OC

H,

I1 a

M

. 114

-115

" 50

2

30

M. 1

10"

(d.)

1

3 0 0

CO

OC

H,

CO

OC

H,

I1 a

14

C

OO

CH

, C

OO

CH

, C

OO

CH

, Ir

a..

47

3

CO

OC

H,

m m m 0. 8

h a hGJ

L - s 2 s

v

W L - 3 r ( I I

m 3 3

L d c d

3 3 x x

u u

Ern m u

Ern Ern u u

zrn Ern u u

- l e a

G / I x c -

m W c Ld * 4

.3 i-'

.3

a" m a,

a, w

2

4 m

4 4 0

E

w o m m '3 8 2 5 9 5 5

'e:

2

e:

2

633

% m

I m m rl

r(

i 0"

F d

V

m co m

$ 3

m

& N s

3 0 N 3 I I

w o 3 0 N 3

a m

d

2 3

mi V

o) t-

2 2- m

I

m rl

N m 3

a

cd

2

In

V

L% 0 .3

i

W 3

t-

u3 3

W W 3 3 L- L-

N P

k=

m* V

.cI N P P 9

Liq u

Ern V

E m m m m m m m

11

C6H

5 H

12

dN

oz

H

HO

OY

H3C

14

a

H

c Li

H5

V b

2 M

. 64"

V b

2-IX

6H

5

V b

2 M

.115

"

CH

3 vn

1 M

. 111

"

CH

3 V

b2

720

72

0

720

66

8

-H,O

: M

. 79"

B. 1

68-1

70"

/20

65

6

B. 1

62"/

15

15

O

CH

3

H

-3

V b

2 M

.49

"

65

6

B. 1

76"

/15

16

C

H3

CH

3 C

H3

IV a

M

. 30-

31"

51

V b

2 B

. 108

"/1

3 51

Ag

salt

Ba

salt

Eth

yl e

ster

: B

. 32

5"

Pic

rate

: M. 1

10-1

11"

17

C6H

, C

H3

CH

3 V

b2

M. 3

4"

6 84

B. 1

81"

/15

ua W

18

C

GH

5 C

H,C

H,

CH

3 V

b2

M.

92"

663

UI

TA

BL

E 4

0b.

N-U

nsu

bst

itu

ted

3 (o

r 5)

-Hal

opyr

azol

es

I H

A)

X =

C1

N.

R

R'

Met

hod

s of

sy

nth

esis

M

.p.o

r B

.p.

Ref

eren

ces

Der

ivat

ives

H

C6H

5

H

-

H

V b

2

f

V b

2

f

VII

I

V b

2

V b

2

V b

2

1' b

2

M.

115"

; 119

" 8

4,6

96

N

a sa

lt

B. 2

58"

708

*HC

1: M

. 137

"

B. 1

38"/

15

Ag

salt

M

. 142

" 79

,704

B. 2

95"

79

-HC

1: M

. 131

"

B. 1

83-1

86"

/12

M. 1

80"

704

M.

190"

27

5

B.1

15-1

16"

/0.0

01

1150

B. 1

15-1

16"

/0.0

01

1150

B.1

17-1

20"

/0.0

01

1150

8 C

H,(

CH

,),C

H,

H

9 C

H,

CH

,

V h

2

B.

132-

135"

/0.0

01

1150

V b

2 M

. 12

1.5-

122.

5"

51

,88

3

V a

-M

B.

251-

252"

51

14

6"/1

4

10

C

H,

gH

5

V h

2

M.

115-

116"

7

9

*HC

l: M

. 14

0-15

0"

B) X =

Br

11

CH

,

12

C

,H5

H

I11

b

M.

127-

128"

50

8

H

V d

2

M. 1

46-1

47"

81 6

VI

h 81

8

C)

X=

I

13

H

H

V

d2

M

. 72-

73"

864

a

14

CH

,

15

H

H

XIX

a M

. 15

9"

503

-(=J

Vd

2

M.

180"

61

5

16

C

H,

CH

, X

IX a

1

M.

140-

141"

50

3

TA

BL

E 4

1.

4-H

alo

py

razo

les

A) X =

C1

Met

hods

of

N.

R

R'

R"

syn

thes

is

M.p

.or

B.p

. R

efer

ence

s D

eriv

ativ

es

1H

2H

3n

4

CH

,

5

CC

l,CC

l,CH

,OH

C6

H5

H

C6

H5

H

H

H

n H

H n H

n

la

V c

8

VI

b

XIX

a

XIX

a-I1

1 b

, d

XLY

a

XIX a

IV a

IV a

-XIX

a

Ia

I11

d

v h

2

VI

b

XIX

a

M. 7

7"

B.

220"

M.6

5-66

"

B.

116-

118"

/12

M.

102"

B.

193"

/11

B.

167"

/756

M.1

19"

M.

75-7

5.5"

84 7

504

84 7

504,

55

6,6

40

556

51

,50

4

54

64 0

5 04

32

9,8

47

85

8

10

59

80

1,8

47

74

,44

8,9

48

'HC

1:M

. 17

5-17

7"

Pic

rate

: M

. 15

1.5-

152.

5"

H

H

Ia

VI

b

XM

a

vc

XIX

a

IV a

XIX

a

1V a

XIX

a

M.

145.

5-14

6.5"

84

7

84

7

51

,44

9,7

39

504

92

51

51

54

51

CH

, M

.117

.5-1

18.5

"

B.

220-

222"

M.1

08-1

10"

B.

178-

179"

.HC

1: M

. 16

0-16

4"

Pic

rate

: M

. 19

2"

'HC

I : M

. 19

6"

-HC

I: M

. 61

"

Pic

rate

:M.1

17

.5"

9H

10

CH

,

CH

,

H

gH

5

CH

,

11

CH

,

12

CH

,C,H

,

H

H

IiH

5

CH

,

B.

153-

156"

/12

B.

288"

.H

C1:

M.

115-

117"

Pic

rate

: M

. 10

1 -1

02"

-HC

I: M

. 14

5"

Pic

rate

: M

. 10

5"

13

C

H,

H

I11

d

IV a

XIX

a

IV a

XM

a

B. 1

77-1

78"

B.6

8.5"

/10

504

51

51

54

51

14

CH

,

15

C

H,C

,H,

gH

5

H

C H

, H

B.

163-

165"

/9

B.2

81"

-HC

1 :M

.110

-112

"

Pic

rate

: M

. 94

-96"

16

C

,H5

C H

C 1,

H

V

I b

M.

56"

881

B.

131-

136"

/0.3

B.

113-

115"

/35

51

17

CH

, IV

a

Pic

rate

: M

. 14

2-14

3.5"

; 14

6-14

7"

XIX

a

VII

I-X

IX a

B.

85"/1

5 4

38

B.

112-

115"

/7

504

ul 18

C

H,

W

W

,CO

OH

1

9

-CH

CH

,CO

OH

cc1,

CH

, IV

a

M.

191"

44

9

I

v1

.e * > .- a"

m"

m m l - t - t - t-

i W

N N N N N N 3 3 3 3 3 3

m N ,-

m N ,-

" I F %

L m

h 3 t- W 3 3 3

I I

iD m * 3 3

3

l- W 3

t- N 3

& m I

m

3

d

d

m N 3

(0 m 3

3

x

L m 3

I W m 3

l i

?? Ern v v z? V

z? ?? sq V 0 0

m N

w o r m N N N

640

m

P

CI

XM

a

93

5

.HC

1 :M

. 14

7-14

8"

Pic

rate

: M

. 19

5-19

7"

B) X= B

r

32

H

33

n

34

H

35

CH

,

36

CH

,C,H

,

39

0

.r

H

H

CH

, H

CH

,(C

H,)

,CH

, H

gH

5

H

H

H

H

H

H

H

H

H

H

H

Ia

M

. 93

-94"

VI

a-V

b2

M

. 96-

97"

XIX

a

B. 2

50-2

60"

XIX

a-II

I b,

d

XIX

a

M.

76-7

7"

XIX

a B

.190

"/3

XIX

a

M.

116-

117"

XIX

a-I

11

b

XIX

a

B.76-78"/18

XIX

a M

.44-

45"

B.

169-

170"

/20

IV

a M

. 192

-193

"

Ia

M

. 81

": 8

2.5"

I11

b, d

B

.293

-295

"

V d

2

XM

a

v f

l

VII

I M

. 84

.5-8

5"

84 7

352

-HB

r : M

. 22

2.5"

.HN

O, : M

. 18

4.5"

(d

.)

20

7,2

11

556

51

,74

,55

1

'HB

r: M

.135

"

Pic

rate

: M

. 15

8'

594

Pic

rate

: M

. 68"

88

,91

,55

3

.HB

r : M

. 18

6"

88

50

8

515

507

604, 847, 32

9.H

C1.

PtC

I,.1

/2H

,0:

M. 1

60-7

0"

11

2

7 97

10

7

199

199

TA

BL

E 4

1. (

con

t.)

m

Met

hod

s of

N

N

. R

R

' R

" s.

ynth

esis

M

.p.

or

B.p

. R

efer

ence

s D

eriv

ati

ves

Q

H

H

42

H

C

H,

43

H

44

H

45

H

46

H

47

H

48

H

49

H

50

CH

,

CH

,

gH

5

gH

5

gH

5

gH

5

+C

Ih

gH

5

H

.XIX

a

H

la

H

XIX

a

CH

3 I1

1 a

1' c

XM

a

XIX

a-I

II a

gH

5

VI a

-XIX

a

XIX

a

gH

5

Ia

CH

, 11

1 b

M.

168-

169"

M.

90.5

-91"

M.1

17"

M.

123"

M.

93-9

6"

M.

198-

199"

M. 2

21"

M. 2

23"

M.

178"

M. 2

28"

M. 17

2"

M.

38-3

9.5"

19

9

84 7

380

10

33

504

73

9

'HC

l.AuC

1, : M

. 12

6-12

8"

.2 B

r : M

. 14

2-14

4"

'HB

r : M

. 17

4"

76

8

Pic

rate

: M

. 19

7"

70

*H

Br : M

. 205

"

92

,95

5

42

7,5

29

427

427

427

e

427

427

51

'HB

r : M

. 12

5-12

6"

In

0

N N - % 2 3

l 1 , b

m t- i

v) t- 4 cn i m

cd cd i

& m

I In m

i

m

Ln

xu V X

z? V

Lr- z X V

3: z X X X

0) In m In t- u3 (D o Lo In

643

0 m -

l l

- I I c

v il I

xm $ m U Y

X 8

644

71

CH

3 fi

H5

VII

I M

. 18

0"

130

XIX

a M

. 15

4"

130

CH

3 fi

H5

XIX

a

XM a

XM a

XM a

XIX

a

M.

116"

M. 5

8-59

"

M.

158"

M. 1

42"

M.

149"

387

80

387

571

523

74

C,H

5

YO

2

fiH

5 fi

H5

76

C,H

,

I1

C,H

,

- F-!

I8

'7' H

XM

a

M.

193-

204"

94

1

I9

XIX

a

M.

124-

125"

93

5 'H

Br

80

H

H

H

V d

2 M

. 10

8.5"

56

1

XIX

21

1,5

03

81

H

CH

3 H

III

b M

.185

-187

"

73

9

-HC

PA

uC

l,

m

XIX

a

503

*HC

P1/

. RC

1,

Ic1 u1

82

CH

, H

H

X

IX a

11

1.64

-65"

50

3

TA

BL

E 4

1. (

cont

.)

R

Met

hod

s of

R

' R

"

syn

thes

is _

_

83

C

H,O

H

/CH

z-C

Hz\

84

-C

HzN

C

H2

\CH

,-C

H ,/

85

g

H5

86

H

87

CH

,

88

+ nq N'

89

a

H

H

H

H

IV a

IV a

XIX

a

VC

d2

XM a

111

a-X

IX

a

V d

2

XM a

XIX

a

M.p

. or

B.p

. R

efer

ence

s D

eriv

ati

ves

M. 9

0"

50

0

M. 8

9"

50

0

M. 7

6.5

"

95

0

M.

137"

50

4

73

9

73

9

94 3

M. 6

5"

556

M. 1

96-2

02"

94

1

M. 1

35"

93

5

,2C

1: M

. 85-

88"

'2Br : M

. 78-

81"

-HC

I:M

.19

6"

.HC

l.IC

l: M

. 11

1"

-HC

I-A

uC

l, :

M. 1

74"

.HC

l.'/

. P

tC1,

: M

. 215

-220

"

TA

BL

E 4

2.

5-H

alop

yraz

o?es

-

N

~

1

2 3 4 5 6 7

m

51

-4

I

A)

X =

C1

Met

ho

ds

of

R

R'

R"

sy

nth

esis

M

.p.o

r B

.p.

Ref

eren

ces

Der

ivat

ives

C6

H5

H

a

H

HO

OC

CH

3 C

6H

.5

CH

,CH

3 C

H3

CH

,CO

OH

C

H3

111

b

V b

2

V b

2

VII

I

IVa

V b

2

IVa

V b

2

IV a

IVa

B. 2

50"

Oil

M.

125"

B. 1

57-1

58"

M.

62"

B.

296-

297"

M.

167"

M.

19

gC

674

674

667

667

84

,95

,88

3

84

79

,68

3

683

84

713

.HC

10

4:M

.14

8-1

49

"

. HC

1: M

. 95

"

. HC

1.l/z

PtC

1,.

H,O

: M

. 19

3"

. HC

IO, : M

. 99"

Ag

salt

Ba

salt

Na

salt

NH

4+ s

alt

Eth

yle

ster

& t- 3

N P

? c

m m m

II m % $ V v v

3 N 3 3

0 i

2 V

$ 2 v v

Ln 3 m e 3 3

b t- I

m 0 3

i

x x x m x x X m m X z

3 N - 0 3 N m 3 t-

3 W 3

W N

v) N

m q N N N N

649

i t -

w t - c a d t-

3 L-

m X

0 m rn N

650

W L- 3

s W P- i

3 3 3 U Y m U Y

W 3

W (D

3

Fd

z7

d

V

V

z7

5

V

m 3 P-

b L-

UY P- I

s

Ei k-

d

D?

V

u

m 3 P-

i N i

i

l?

D? V

m 31 V

W * i u a * * 0 *

65 1

t- W W 2 : : c - t -

N n * b * N N Q P

W e e m * *

m ^ m e m o ) o ) L - L - 3 L- * 3 w w t- iD w t -

w m o 1 % e * m

652

TABLE 4

4.

3,4-

Dih

alop

yraz

oles

N.

R

1

2 3

4 5 6 7 8 9 10

11

12

13

14

H

H

H

H

H

H

H

H

H

H

'6*5

CH

3

CH

3

CH

,CH

,

R'

H

H

CH

3

CC

l,

CH

3

CH

3

CH

3

C6

H5

C6

H5

GN

o2

X

Br

I c1

c1

c1

c1

Br

c1

c1

c1

Br

c1

Br

c1

X' -

Br

I c1

c1

Br

I Br

c1

Br

Br

Br

Br

Br

Br

Met

ho

ds

of

syn

thes

is

XIX

a

vc

WC

a

* XIX

a-V

III

XIX

a

XIX

a

XIX

a

XIX

a

XIX

a

VII

I

XIX

a

XIX

a

XIX

a

WC

a

XIX

a

M.p

. or B

.p.

M.1

33

.5"

M. 1

62-1

63"

M.

115-

117"

M.

12

8"

M.

166-

167"

M.

140"

M. 1

52"

M.

145"

M. 9

5-96

"

M. 9

0"

M.

130"

M.

83.5

-84"

M.

56"

M.

74"

M. 3

9"

Ref

eren

ces

Der

ivat

ives

508

50

3

50

4,6

96

765

504

696

696

508

704

704

Ben

zoyl

der

iv : M

. 70

"

Ben

zene

sulf

onyl

der

iv : M

. 12

6-12

7"

. Br,

: M

. 18

6"

704

10

8,9

50

88

3

525

88

3

15

CH

,C,H

, C

H3

C1

Br

XIX

a

M. 62-63"

84

B. 195"/13

16

C,H

, C

H3

C1

C1

V b

2-X

IXa

Oil

654

17

C,H

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M. 194"/15

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m 3-methyl-5-chloropyrazole w

ith

dil

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E 45.

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X' N

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ds

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R

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X'

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thes

is

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efer

ence

s D

eriv

ativ

es

0,

cn

cn

1H

H

B

r

Br

I11

c M

. 151"

506

2H

'C

jH5

Br

B

r

Vfl

M. 157-157.5"

389

3 C

,H,

H

c1

c

1

V b

2 M

. 25-26"

706

B. 170-172"/16

4 C

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H

Br

Br

Vb

2

M. 5

0"

674

5 C

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, c

1

c1

V

b2

B. 155"/16

706

6 C

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, C

1 c1

V

b2

M. 81"

71 1

3 - w c o r r m w w

d p x

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8

8

X

w m

W n I

m n

r'

d

8 8

m L

z7 V

g 0

m m 3

ln t- I

w t-

i

3 w

k-

L F9

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w

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N O I C O N F J r m o t - w m t -

B

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u)

xu V

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656

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m

c o o 3 a m W W W - t-t- m r m m m W W m a n m m

c- (D

m t- W

m t- (D

N d r dr 0 3 3 t - l - t-

N m

s

3 CI] 0 N m 3 m 3 t- 3 n d r m W

3 3 3 3 N 3

6 5 7

m c

c .3 Y

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a"

8

2

m u

W * 19 m n

19 m m

10 m m 3

W m i

m m

m

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2

t- 3 t- t- 3 L-

L - t - M M c - t -

658

TA

BL

E 4

7.

3,4

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rih

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py

razo

les

N.

R

X

X'

X"

1H

B

r B

r

2H

I

I

3 C6H5

C1

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4 C6H5

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5 C,H5

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TA

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E 4

8.

Hal

odi-

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r B

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Ref

eren

ces

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ivat

ives

V b2,

i, X

IX a

M

. 180

-181

"

474

XIX

a

M. 1

84"

50

8

XIX

a

M. 2

21"

50

8

XIX

a

M. 8

2"

674

XIX

a

M. 8

5"

674

XIX

a

M. 1

06-1

07"

1

08

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4

M. 12

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-

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s of

sy

nth

esis

M

.p. o

r B

.p.

Ref

eren

ces

Der

ivat

ives

m

UI

W

V b2

M.1

66

-16

7"

9

62

XIX

a M

. 159

-160

"

377

L- L- m

m t- N

N r- N

I

5

d

8

k % n u

t- t- m

d

m 0 L-

u !5

3 Ln 3

s

N m N

s

*

50

660

m

2 M

$

H

V

c R

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B .- a

u 8 Y

fi m 3

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l d m

w *

3 E

m 0 LD n 3 t-

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a I

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Hal

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Sal

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R

R'

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Y-

Met

hods

of

syn

thes

is

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.or

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. R

ePer

ence

s D

eriv

ativ

es

1H

2 C

H,

H

CH

, H

B

r XIX

a

M. 1

26"

508

CH

3 C

H,

CH

, B

r X

IX a

50

8

1) x

= c

1

N.

R

R

R"

R"'

Y-

Met

hods

of

syn

thes

is

M.p

.or

B.p

. R

efer

ence

s D

eriv

ativ

es

1 C

H,

CH

3

CH

, H

I

IV c

M

.219

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.)

51

Pic

rate

:M.

129.

5-13

0.5"

2 C

H,C

,H,

-3

CH

, H

I

3 C

H,C

,H,

CH

3 H

C

H3

I

4 C

H,

CH

3 C

H,

IV c

M

. 129

-130

" 51

IV c

M

.159

"

51

I IV

c

M. 1

96"

51

M. 1

27.5

-128

"

2) X

= B

I

'GH

S C

H3

H

CH

3 I

Nc

M

. 206

" 88

8

1) x

= c1

Met

hod

s of

sy

nth

esis

M

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r B

.p.

Ref

eren

ces

Der

iva

tiv

es

N.

R

R'

R"

Y

Nc

M

. 172

"; 1

61"

(d.)

6

74

,68

0

M. 1

47"

M. 2

07"

I c1 . C1.

PtC

l,.H

,O

CH

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3 H

H

do

, I

M. 2

09"

674

M. 1

81"

M.2

17"

M.l

56

"(d

.)

674

M. 2

35-2

36"

84

,69

6

M. 2

43-2

47"

M. -

240"

M. 2

52"

84

M. 1

36"

84

,69

6

Nc

c1

. C1.

'/z P

tC1,

I I

C6

H5

4 C

H,

CH

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H

CH

3

CH

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IV c

Nc

Nc

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2

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C1

C1.

HgC

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z M

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20

: M

. 243

"

M.1

32"

5 C

H,

CsH

B

H

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2

M. 1

67"

M. 1

30"

M. 1

36"

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TABLE 49b.

(con

t.)

Met

hod

s of

m

m

P

N

. R

R

' R

" R

"'

Y-

syn

thes

is

M.p

. o

r B

.p.

Ref

eren

ces

Der

ivat

ives

6 C

H,

CH

,CH

, C

H,

H

7 C

H,C

H,

CH

, C

H,

H

8 C

H,C

OO

H

CH

, C

H,

H

CH

,CO

OC

,H,

9 C

H,

CH

2C

6H

5

CH

, H

10

CH

, C

6H

5

CH

, H

11

CH

,

12

CH

,

13

C

H,

14

CH

,

<f'

CH

, H

C6

H5

O,N

o{-k

No.

0

9

I c1

0,

c10

,

I I I I c1

Br

I c1. b

MC

1,

I I I C1

c1.

PtC

l,

I

IV c

IV c

IV c

V b

2

VII

I

IV c

IV c

IV

C

Nc

Nc

VlI

I

IV c

M. 150"

M. 184-186"

M. 208-213"

M.

187-

188"

M. 191-194a

M. 156"

M. 1

30"

M. 1

60"

(d.)

Dec

. 120-175"

Dec

. 197-200"

Dec

. 177"

M. 2

18"

M. 207"

M. 196.5"

M. 138"

M. 145"(d.)

M. 288"

M. 169"

84

84

713

113

51,8

4

654.983

654

654

654

716

716

720

720

120

u = v u

2 2 2 2 0 v u u 2 2 2 2

m m m

d d Ern v u u

L1

d r" 4 u u v

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a x

d x" u u

d s " v LU

m m - 3

T T r n T

0 - N O N " N

665

TA

BL

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9b.

(con

t.)

m

Met

hods

of

m

m

N.

R

R'

R"

R

"'

Y-

syn

thes

is

M.p

. or

B.p

. R

efer

ence

s D

eriv

ativ

es

24

C

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CH

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H

c1

I c1

. lb

PIC

lq

26

C,H

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H5

CH

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30

CH

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H,C

H,

31

CH

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OH

C

H3

CH

2CH

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OC

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CH

, H

CH

, H

CH

, H

CH

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CH

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I3r

1 I I c1

VII

I M

. 194

"

721

Nc

M

. 172

"

72

1

M.2

22"

Nc

M

. 17

2"

721

V b

2 M

. 105

" 53

6

VII

I M

. 110

"

687

IV c

M

.231

-232

"

V b

2

IV c

IV

C

IV c

Nc

IV c

IV c

IV c

M. 2

32"

M. 23

4"

M. 24

5"

M. 1

53"

M. 2

64"

M.2

25"

(d.)

M.1

87-1

91"

M. 1

42"

M. 13

6"

M. 13

8"

71 7

717

717

71 7

88

3

84

,69

6

713

713

661

33

CH

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,

34

CH

3

35

C

H,

36

CH

,

37

C,H

,

38

C,H

,

39

C,H

,

40

C,H

5

H3

C

41

23

H

I

CH

3

I O2N

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/ 0

9

I c1

c1

I C1

.h P

tC14

c1

Br

I c1

I c1

I c1.

RC

1,

C1.

HC

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I

IV c

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Nc

V b

2

VII

I

IV c

Nc

Nc

Nc

VII

I

IV c

VII

I

Nc

IVC

M. 20

0-21

6"

M.

184-

188"

(d.)

M. 12

4"

M. 1

65"

M.9

4"

M. 23

5"

M.1

62"

M.

197"

M. 1

76"

M. 14

8"

M. 16

7"

M. 2

13"

111.

203"

M. 23

6"

M.

187"

84

51

51

685

719

719

719

719

719

719

71 9

703

703

667

c1

vni

M.-

214"

67

8

Dr

Nc

M

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.)

678

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. 146

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2 67

8

I IV

c

M. 2

33"

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M.5

7"

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E 4

9b.

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t.)

m

m

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R"

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sis

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eren

ces

Der

ivat

ives

43

-3

CII

, H

I

M.

259"

71

4

44

C,H

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H2C

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CH

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C

1 V

III

M.1

82"

648

Br

Nc

M

.196

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8

45

C

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3

CH

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Br

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M

. 23

0"

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3)

X=

I

46

CH

,

47

o

m2

48

C

6H

6

49

C

,H,

50

C

6H

5

52

CH

,

63

C

H,

54

C,H

,

CH

3

CH

3

CH

,CH

,

CH

,CH

,CH

,

CH

2CH

=C

H2

CH

2C

H3

C6

H5

C6

H5

CH

2C

H3

CH

3

C,H

, H

CH

, H

CH

, H

CH

, H

CH

, H

CH

, H

CH

3

CH

,

CH

, C

H2

CH

3

CH

3

CH

,

CH

, C

H,

I I c1

I I c1

I I I 1

c1

I I

TV c

-V

c8

IV C

-V c

8

VII

I

N c

-V

c8

IV C

-V c

8

VII

I

N C

-V

c8

N c

-V c8

IV C

-V

c8

N c

-v c

8

VII

l

N c

-V

c8

IV C

-V c

8

M.

188-

190"

79

M.

229"

67

8

M.2

22

"(d

.)

702

M.

240"

(d.)

I0

2

M.

225-

226"

5

3

648

M.

195-

194"

M.

203"

(d.

) 64

M.

231"

7

11

M.2

17"

684

M.

196"

6

63

M. 1

90"

719

M.2

22-2

23"(

d.)

719

719

N.

R

R'

Met

hod

s of

R

efer

ence

s D

eriv

ativ

es

R"

R'"

R

""

Y-

syn

thes

is

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.or

B.p

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C6

H5

C

H3

C1

H

c1

c

1

V b

2

1 N

c

2 C

H3

CH

3 C

H3

Br

c1

B

r N

C

3 t

>B

r

CH

3 C

H3

C1

c1

I

Nc

'CsH

5 C

H3

CH

, B

r c1

I

IV c

'bH

5

CH

3 C

H3

I c

1

C6

H5

C

H3

C1

Br

c1

I I

IV c

-v c

8

SO,C

H,

IV

c

M.

155-

158"

M. 1

66-1

67"

M. 1

99-2

03"

M. 2

30"

M. 2

29"

(d.)

M.

178"

M. 2

10"

692

692

84

714

645

702

692

692

m

-2 0

TA

BL

E 5

0.

N-N

itro

pyr

azol

es

N.

R

R'

R"

Met

hod

s of

sy

nth

esis

M

.p.

or B

.p.

Ref

eren

ces

Der

ivat

ives

1H

H

H

X

IXb

M

. 93"

49

6

C6

H5

H

H

3 C

H,

H

CH

,

XM b

M. 1

22"

310

XIX

b

M. 6

6-67

" 49

6

4 C

HzC

H3

H

CH

zCH

3 X

Mb

O

il

496

5 C

H,

CH

3 C

H3

XIX

b

496

TA

BL

E 5

1.

3-N

itro

pyra

zole

s

R" H

'lrrN

oZ

N/N I

N.

R

R'

R"

Met

hods

of

syn

thes

is

M.p

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r B

.p.

Ref

eren

ces

Der

ivat

ives

1H

C

6H

5

H

2H

H

3H

H

+I

I1 c

M

. 209

-210

" 81

8

V d

l 81

6

VI

b

818

* M

. 27

2-27

4"

436,

615

534

~H

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C6

H5

H

H

I1

1 d

M. 9

7"

ul

C6

H5

4

cL

6 C

6H5

H

CH

, X

IVa

M

. 96"

H

CH

,CH

, X

IVa

M. 78"

1133

422

422

422

HC

1: M

. 30

0"

CH

31 : M

. 25

7" (d.)

. CH

,C1

: M. 2

90"

(d.)

. CH

,OH

: M

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7" (

d.)

Pic

rate

: M

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2"

* Fro

m n

icot

ine

wit

h HNO,

n Y

X

m

m

3

x x x 31 X 31

m X Z x X X

N m e m W t-

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2a. (

cont

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m 2 N.

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Met

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Ref

eren

ces

Der

iva

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es

1133

8 9 10

11

12

13

14

15

16

17

18

H

a c1-

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CH

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OC

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1133

H

1133

H

1133

H

IV a

IV a

M. 9

9.5"

M. 5

6"

500

500

CH

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CH

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H

H

M.

85"

500

IV

a

H

1042

38

1,4

62

,47

5

312

IV a

Ia

XIX

b

M.

132-

135"

M. 1

26-1

27"

M. 1

29-1

30"

H

H

CH

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OH

'IjH

5

H

H

312,

381

312.

381

Ia

XIX

b

M.

148"

M. 1

51-1

52.5

"

H

M. 1

55-1

56"

38

1

381

381

Ia

v1n

XIX

b

H

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3 i

7 m f

S $ w

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X

X

x m X m X

X 5:

m X

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N N

Q, 3 : : F : N

675

N m n N m m

cu m m P

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m P 3

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ence

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ativ

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X

IXb

M

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M. 9

1-91

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496

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4.

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Met

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ence

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__

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__

__

_

~_

_

0

1H

X

IX b

61

6

1133

,HC

k M

. 13

0"

680

0 i m m

TABLE 55. (c

ont.

)

m

Met

hods

of

Ref

eren

ces

Der

iva

tiv

es

N.

R

R'

R"

sy

nth

esis

M

.p. o

r B

.p.

03

24

25

26

21

28

29

30

31

32

33

34

35

C6

H5

l

Ia

Ia

Ia

Ia

Ia

Ia

Ia

la

Ia

M

. 137.5"

Ia

M

. 130"

Ia

M. 135"

M. 153-154"

M. 100'

Oil

M. 109. 5"

Dec

. 170"

Oil

M. 92-93"

M. 165"(d.)

M. 88-89"

910,1053

910

910

1144

1080,1141

1129

910

642,1129

1129

642,1129

642,1129

642,1129

3 t- m

m W 3

z!

V

In

3 u

< u

In

% u

W m

683

t- W i (D

3 3 -

m - 0 t-"

m m m N W m

3

5: 3 W

Ln 0 In

3 o i L n ( 0 ln W

m t- i

t- t- i

I

s

m m w m

6 6 6 6

o m m x u v 8 8

O n 2 B x x

8 8 8 8 v u U U

0 x x x x u x x x x x x

m x x x x x m

2" U x

N

m m

( 1 - r w t - m

684

13

14

15

16

17

18

19

20

21

22

23

24

25

26

g 23

UI

28

CH

, H

C

6H

5

CH

,CH

, H

C

H,C

H,

C6

H5

H

C

H,

C6

H5

H

c6

H5

CH

, C

H,

H

H

-CH

~C

H(C

H,)

CH

~C

H~

-

-CH

ZC

HZ

N<&

CH

3 --

CH

,CH

,CH

,CH

,

-CH

2CH

2CH

2CH

2-

H

H

H

H

CH

,(C

H,)

&H

, H

H

H

H

CO

CH

,

CO

CH

,

CO

CH

,

CO

CH

,

CO

CH

,

CO

CH

,

CO

CH

,

CO

CH

,

CO

CH

,

CO

CH

,

CO

CH

,

CO

CH

,

CO

CH

,Cl

CO

CH

,Cl

CO

CH

,Cl

CO

CH

,Cl

m c

XX

Ve

XX

V e

-n

XX

V e

-VIl

I

Ia

XX

Ve

XVm

b

XX

Ve

XX

Ve

XX

Ve

We

XX

Ve

XX

V e

-VII

I

XX

Ve

XX

Ve

XX

Ve

XX

Ve

XX

Ye

B. 8

8-89

"/4

0

B. 8

4"/2

3

B.

70"/

12

M. 6

8"

M. 1

60-1

61"

M. 4

5.5

-46

.5"

B.9

4O/1

2

M.4

3"

B.1

58-1

60"

M. 87"

B.

226"

/10

M. 88

'

B. 1

90"

B. 1

43"/

17

M. 8

2.5

-83

.5"

M.

154-

155"

B.1

30"

/15

B.

170-

172"

/52

M, 3

3-34

"

B. 1

40-1

45"

/0.0

2

M. 6

7.5-

68"

M. 15

5"

947

61

,72

6,9

67

505

505

67

501

67

955

1036

523

61

74

96

9 57

725

1148

726

598

TA

BL

E 5

6a.

(co

nt.

)

a

m

X

m

N.

R

R'

R"

Met

ho

ds

of

syn

thes

is

M.p

. o

r B

.p.

Ref

eren

ces

Der

ivat

ives

29

CH

,

30

CH

,

31

CH

,

32

CH

,

33

CH

3

34

H

35

H

36

C

H,

37

CH

,

38

C

,H,

39

CH

,

40

CH

,

41

CH

,

42

CH

,

43

C

H,

44

CH

3

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

CO

CIi

,SH

CO

CI1

20C

GH

s

CO

CH

,NH

,

CO

CH

,NH

CH

,

--C

OC

H,N

HS

Oz~

'> ,-

CH

?

CO

CO

OC

,H,

CO

CH

,CH

,

CO

CH

,CH

3

CO

CH

2CH

3

CO

CH

zCH

j

CO

CH

,CN

CO

CH

,CN

--C

OF

IIC

H3

la

la

VII

I

VII

I

Ia

XX

VC

XX

Ve

la

XX

VC

la

XW

II b

XX

Ve

Ia

la

la

Ia

me

Ia

M.

118-

119.

5°

M. 8

5-87

"

M.

101-

102"

M. 9

5"

M.

112-

113"

B.

155-

156"

/16

B. 1

48-1

50"/

48

B.9

9-99

.5"/

24

B.9

4"/1

2

M. 33

-34"

111.

77-7

8.5"

M.

118-

121"

M.1

53-1

54"

M.

144.

5-14

5.5"

111.

143.

5-14

4.5"

B.

126-

128°

/40

M.

34-3

5.5"

87

6

878

726

726

87

7

72 5

725

363

726

67

67

67

875

872

877

877

726

67

.2H

C1:

M

. 13

4-13

5"

Pic

rate

: M

. 15

1"

Pic

rate

: M

. 10

0"

Pic

rate

.HC

1: M

. 24

0"

.HC

lO.,:

M

. 51

"

-BIO

,: M. 15

7-15

8"(d

.)

c - m m m m m C t - C c W

m N Lo

m N in

in m 7. - 0 i i

m m N in LD

03 0 m 7. 0)

i i e

ci a m a I - e I

d m o N C i n m

s " $ $ U U U

s" U

r 9 r a

c1 9 51 a d d U 0 U U U

B U

X s E r n 3: r

(1 t- m

i

m d d d d d

F m

Z F L ? z a m 0 t - t - t - t- t-

m m m m m m m i~ i~

m 0 c m

N 0

I m rn 3

2

m 2.2: m m s m m

0 m V u u u u u

m o d

0

am U

l? U

1;" d d d

W N * (0 i?

ln L o r n iD (0 L D i D ( D t - m

688

d

m F

a i

d W N W z

m

d

m N F m t- m c W

(D co

i i i i

d

F co

3 W

i

d V

ln W

2" V

d

W c- W 0

m X 2" 2"

V V V

z m X 51

2" 2"

F c-

U U U d u d

- 01 W m W

m X V

N c

689

TA

BL

E 5

6a. (

cont

.)

Met

hod

s of

0,

(D

R

R'

R"

X

sy

nth

esis

M

.p. o

r 9

.p.

Ref

eren

ces

Der

ivat

ives

0 N.

74

H

75

CH

3 H

C

H3

76

CH

3

77

CH

3

78

H

H

CH

3

H

-3

H

H

79

-3

H

H

80

CH

,(C

H,)

,CH

, H

H

81

CH

,(C

H,)

,CH

~

H

H

82

CH

,(C

H&

H,

H

H

XX

Ve

M. 8

1"

870

a

XX

V e

l 87

0 a

Ia

M

. 129

-132

"

870

a

XX

V e

87

0 a

XXV e

l 87

0 a

CO

C,H

,

CO

CsH

5

CO

C,H

,

CO

C,H

,

Ia

M

. 75"

XX

Ve

Ia

M

. 73

"

870

a

870

a

8'10

a

483,

55

6,7

24

m

e

M.

46"

B.2

81"

B. 2

20-2

25"

/60

B.1

40"

/11

me

B

. 155

-157

'/14

65

XX

Ve

B

. 17

4"/2

.5

534

9. 1

35-1

37°/

0.

001

1148

B. 1

40-1

45"

/0.0

02

1148

XIN

e

XX

Ve

.HC

10,:

M

.161

-162

"

83

C

H,(

CH

~)~

~C

H,

H

H

84

C6

H5

H

H

CO

C,H

,

CO

C,H

,

XX

Ve

XX

V e

B. 144

-146

~m.0

01

1148

M. 57-59"

212,955

M. 64-65"

B. 20

0-20

2'/5

94

7

B. 1

58"/

2 442,126

M. 88-89"

67

M. 83-84"

67

67

67

Pic

rate

: M

. 160"

CO

C,H

, 85

C

H3

H

CH

3 l

a

XX

Ve

la

Ia

VII

I

XX

V e

86

CH

3

87

C6

H5

CO

C,H

,

CO

C,H

,

H

H

CH

.3

88

H

~ C

H,C

H,C

H,C

H,

CO

C,H

,

CO

C,H

,

XX

V e

M. 58.5-60

48

B. 208-210"/13

B.

20

ZY

12

48

48

89

H

-CH

,CH

,CH

,CH

(CH

&

XV

III

b

XX

V e

Q

-CH

2C

N*

XX

Ve

96

90

H

C

OC

,H,

M.141"

Oil

91

-CH

(CH

,)C

H,C

H,C

H,

~ H

C

OC

,H,

Ia

48

873

813

92

C

H3

H

CH

, l

a

XXV e

d

H

-co [)

93

H

H

CH

3 I

a

M.1

30"

67

94

H

H

'6"5

I

a

M.151-152"

67

m

+-

95

In -c

o (3

H

CH

3 H

I1

1 b

B. 95

"/13

60

O h w w h tn

Q

B

n xw

h m

h 0 W 0 0 w 0

0

: : s

n

9 2" E U 0 V d

U X X X B

n

2 xw X U U

3 0 0 z 3 m m m m

2" u x

B U

N m - 2 a a

& 3 3 4

& 3 3

i

& I m CC

i

P Ln

3 Ln

I

i

n h CC

N Ln -r 3 0

3 3 3 3 e 0 3

3 3 3 3 3

h m * 0 o m S P 3 i O S

6 93

c W

&

m

t- I t-

i

d 3

3 4 7

% U

X

Xm U

0 N 3

c W

P

i m W

Q

E

a?

rn 0 0 2 E t - t- W m m

0 0 i

I N

3

N

i n 0

i i

w W

G d V

X

B V d

U

d N 3 rn N 3

W '0,

W m m

m m i s 2 2 m m

W

c1 m N

m

m N 3

i W m - i

W

2 6 o w a,

m " X

L9 7% 0

Y

(c

m V

m

U

m

3: c? a X'

U

m

6 V

i m c

m

m s: ie, m 21 m

z W N c

m

:: m

t- N " Ln

N - 695

w In 0 3

0 In

W I

m

W

&

mi

z;

Q,

k mm 8 u

I

m

mm u D? u

3 cu

In E- m

696

P

d d d 0 2

s :: x z x

4 x x u x

u?

x 8 L

0 a

c1 CI w Y w

m m

In W

697

Y 3

rn

2"

m t- 'a

& 0 3 I

m m

z;

V

G

m

u u mm

8 v

m

m

m

m W i

ln I

m w m m w w 3 - m

3 m 3

s

d V d Y C U Y

?!! 8 u

m

r d d w w w w m m

3

t- &

ln I

0 t- rl

i

P C

= 5 b - x

In

?!:

8 8 8 u u 5

m 5 m

0 3

3 rn m 3 3 3

* * *

p* 3

15

H

H

-c

o%

p)-

c,

I1 c

M

. 12

9-13

1"

M.

159"

M.

187-

187.

5"

580

16

H

I11

d 58

4

H

17

H

II

C

580

H

-c,ocH

3

H

18

H

I

IC

M

. 97-

97.5

"

M.

134.

5-13

5"

M. >

300°

580

19

H

20

H

I1 c

58

0

-CH

=CH

CO

CC

&

XV

II b

-VII

I

XX

IV b

XV

II b

-VII

I

375

410

21

H

22

H

23

H

-C(S

O~H

)=C

HC

OC

O-

- C

(NH

C,H

,)=

CH

CO

CO

-

- cc

l=cc

lcoc

o-

375

Na

salt

M.

360"

(d.)

V

III

XV

II b

-VII

I

XX

IV b

VII

I

375

408

408

408

24

H

25

H

- C

(NH

C~

H~

)=C

C~

CO

CO

-

-CH

=CH

C[C

H(C

H,)

,]=C

HC

O-

M. >

300"

M. 1

04-1

05"

I

a

VII

I

635

Br:

M. 1

61-1

62"

635

635

m

26

H

W

(D

Ia

M

. 21

6-21

7"

TA

BL

E 5

7. (

con

t.)

4 0

* N

. R

R

' X

M

eth

ods

of

syn

thes

is

M.p

. or

B.p

. R

efer

ence

s D

eriv

ativ

es

27

C/H=CH

COOH

Q coco

-

***

635

XVII b

-VII

I 27

7 E

thyl

este

r

Met

hyl

este

r:

M. 290-292"

* ** F

rom

3-b

enzo

yl-4

-dia

zo-

5-p

hen

yl-p

yraz

ole or 3 -b

enzo

yl- 4

-ph

enyl

- 5-

dia

zo-p

yraz

ole

by

irra

dia

tion

in

ben

zen

e.

***

Fro

m 5-bromo-6-isopropyl-1,2-diazoazulene b

y tr

eatm

ent

wit

h h

ot a

lkal

i.

Fro

m 0

-dia

zoac

etop

hen

one

by

trea

tmen

t w

ith

NaO

H i

n d

ioxa

ne

at 85", o

r w

ith

NaO

CH

,.

TABLE 5

8.

3-A

cylp

yraz

oles

Met

hod

s of

N.

R

R' R"

X

syn

thes

is

M. p

. or

B. p

. R

efer

ence

s D

eriv

ativ

es

2 C

6H

5

H

CH

,

3 C

6H5

H

H

4 't

jH5

H

CH

,

6 C

6H

5

H

C6

H5

-l

0

-7

C

H,

CH

, H

CH

O

xmn

g M

. 56"

88

7 O

xim

e: M

. 17

7-17

8'

CH

O

CO

CH

,

CO

CH

,

CO

CH

,

CO

CH

,

CO

CH

,

B. 1

15-1

2071

3 S

emic

arb

azon

e:

M. 2

01"

G

uan

ylh

ydra

zon

e:

HN

0,:M

. 20

0"

I1 f

B-1

85"/

22

489

Dip

rop

yl a

ceta

l

888

Oxi

nie

: M

. 16

6"

Id

Ph

enyl

hyd

razo

ne:

M

. 17

3"

Sem

icar

baz

one:

M

. 183

"

Gua

ny!h

ydra

zone

: H

NO

, M

. 15

5"

335

Ph

enyl

hyd

razo

ne:

M

. 182

"

XIV

c

M. 90"

24

4,2

45

, O

xim

e: M

. 17

5"

* 90

9 M

. 56

" 2

46

O

xirn

e-b

enzo

ate:

Sem

icar

baz

one:

M

. 228

"

XIV

b

M.

134-

135"

35

5

XIV

a

M. 8

8"

171

In d

M

. 19-

20"

19

8

B. 6

3.5

-65

"/0

.1

a m

I I m

m 3 W - - W 3 (D

3

X X

m 3

N 3

0 0 a m 3 3

702

Ln 3 * -

zm m o m

( D o c - m 3 3 3

19

C,H

,

20

C

,H,

H

CH

3

'gH

S

'CiH

5

CO

C,H

,

CO

C,H

s

***

M. 9

1"

XX

VI

el

M.

155"

909

Oxi

me:

M. 1

54"

2,4

- din

itro

ph

enyl

- h

ydra

zon

e: M

. 21

0"

184

2,4-

din

itro

ph

enyl

h

ydra

zon

e:

M.

210-

212"

Othe

r 3-

acyl

pyr

azol

es

N.

Com

pou

nd

s M

eth

ods

of

syn

thes

is

M. p

. or

B. p

. R

efer

ence

s D

eriv

ativ

es

22

n5c:3

3cH0

H

5

6

Ia

M

. 138

"

34 8

I1 a

M

. 76

"(d.

) 49

9

***

Fro

m d

iazo

met

han

e an

d a-phenylazobenzoylacetone.

4

0

w

4

0

P

TA

BL

E 59.

4-A

cylp

yra

zole

s

H"

N.

R

R'

R"

~ ~~

~ -

1

CA,

H

I1

2 C

,H,

H

H

3 -

0L

l

H

H

4 O

OC

%

H

H

CH

O

CH

O

CH

O

CH

O

CH

O

CH

O

CH

O

XXV e

2 B. 1

06-1

08"

/20

383

2,4

-din

itro

ph

eny

l h

ydra

zon

e:M

. 264

-65"

mli

: 16

7. 5

" O

xim

e:M

{ sp: 1

35"

V

IE

M. 8

5-

3 80

XX

V e

2

an

ti: 99"

0-A

cety

l0xi

rne:

M { s

vn:

103"

A

ni1

:M. 1

20-1

21"

u-B

rom

odn

il:

M. 1

02'

m-B

rorn

onil

: M. 12

6"

y-B

rom

oa

nil

: M

. 169

"

Dim

eth

ylim

mon

ium

d

eriv

ati

ves

: -c

hlo

rid

e: M

. 85

-86"

-c

hlo

rop

lati

nat

e:

M. 2

28"

XX

V e

2

M. 1

18"

10

83

XXV e

2 M

. 94"

10

83

XX

V e

2

M.

1 80°

3

84

XX

V e

2 M

. 114

' 10

83

XX

III g

M. 75

-16

.5"

88

5 P

hen

ylh

ydra

zon

e:

XX

V e

2

3 85

M. 1

45"

m m

P m- m m

m m m o m r r m m m m m m m

N w

$

8 u

2:

m V

0 0

0 0 u m z 8 0 0

5 8

g g

0 2: U

m

705

TABLE 59. (c

ont.

)

4

0

01

N.

R

R'

R"

X

Met

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Der

ivat

ives

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VII

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XX

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Id

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I

IIIb

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M. 160.5-161.5"

M. 63-65"

B. 181-182"/8-9

M. 121-122.5"

M. 129"

M. 128"

M. 107-108"

B. 331-333"/145

M. 156"

M. 144"

385

812,307

388

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109

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266,301

425

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412

414

Dim

eth

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mm

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M. 170" (

d.)

Oxi

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M. 156-158"

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icar

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dra

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M. >

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A

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M. 129-131"

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M. 142-144"

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M. 94.5"

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M

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rate

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rate

: M

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1

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H

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168"

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XX

VI

b-V

III

M.

176"

XX

III b

159

-2H

C1

561,

860

-2H

N0,

968

Pic

rate

:

1062

P

icro

lon

ate:

M. 1

95-1

96"

M. 2

42"

Bis

- (p

-ace

ta-

mid

oph

enyl

sul-

fo

nyl

der

iv.:

M

. 190

-192

"

326

856

449,

497,

326

-2H

C1:

M

. 195

-200

"

449,

765

326

594

0 b R c-ca 43

O N I n N 0 0 7 4

P

! x

I w 0 3

i 3

3 e O P O

m 5:

Ln

=a U

2 x u

D? m u

u,

=a U r n

ln ( D r

723

w m m n C O P -

El ?

m m P-

0 rl 0 rl

i

rl d

m 0) m d m P-

i

rl d

m co m

cn- m P-

rl d

- I d c d d d d Q

x; m; v v

m m

m 4 :

m

P

z? V

In In

% u % V

e

3 N 3 3

725

TA

BL

E 6

5a.

(con

t).

-1

N

Q,

N.

R

R'

R"

M

etho

ds o

f X

sy

nth

esis

M.p. o

r B.p.

Ref

eren

ces

Der

ivat

ives

NHCHO

NHCONH,

NHCONHC6H5

NHCSNHC,H,

-NH

CS

NH

NHCOCH,

NHCOC,H,

N=CHC,H,

XX

VIb

rn

f

XX

VI

f

XX

VI

f

XX

VI

f

XX

VI b

IMV

I b

XX

II a

1

XX

II a

1

XX

II a1

XX

II a

1

XX

In cl

M. 112-113"

M. 198"

M. 193"

M. 173"

M. 189"

M. 120"

M. 181"

B. 113"

M. 103"

M. 101"

M. 169"

M. 188-189"

710

-H,O: M.81"

710

710

710

710

710

.H,O: M. 94-95'

710

710

710

710

710

710

-HC1: M. 292"(d.)

14

C,H,

15

CH3

16

C6H5

--

NH

~H

-C

O-

CH

~ V

III

Ia

M. 239"

M. 263-264"

M. 102-104"

M. 38-40"

M. 130-131"

M. 153-154"

M. 144-145"

M. 90-91"

M. 125-126"

M. 15

5-157"

M. 160"

M. 218.5"

710

710

556

.2HC1

861,895,763 *H20.

M. 68"

365,895

763

861

918

861

763,895

365,895

910

910

TA

BL

E 6

5a.

(con

t).

Met

hod

s of

sy

nth

esis

M

.p. o

r B

.p.

Ref

eren

ces

Der

ivat

ives

N

. R

R

' R

"

X

-3 N

18

C,H

, C

H3

gH

5

XX

IIIb

M

. 102

-104

"

C

XW

a1

M. 1

58-1

59"

XW

a

M. 1

56"

XW

a

M. 1

94"

XX

II a

M

. 235

"

02N

'

TA

BL

E 6

5b.

4-A

min

opyr

azol

es w

ith

Un

assi

gned

Str

uct

ure

895

365,

895

365,

895

910

910

910

-

Met

hod

s of

N

. R

R

' R

" X

sy

nth

esis

M

.p.o

r B

.p.

Ref

eren

ces

Der

ivat

ives

/CO

-CH

z

'CO

-CH

z C

6H

5

CH

3 C

6H

5

--N

I I

a

M. 1

93"

91

8

M. 1

50-1

51"

91

8

2 2 w w

P 0 m 0 1 t - w m o ~m

a m

E E I 1 * * u u + +

I

X

Xm u

$ N

z Z Z w w w

0 r.3

N * N

>

m

X

z? u

0 0

w w a m

R cd m

s

w r

729

z X X x m m 3:

730

m m W

m m W

m m W

m W

3 t-

m m W

3 L- W O

W W m L- lc

m 3

I W v) m m d 3

Y 8 E Y Y Y E E

X m X m X m 31 m m

m 3

m 3 t- i W

3

* N CT) N N N i N 0 N

73 I.

m W N

b W

z'

X

ln

m 3 Fi

n 4 w m N O W N % Z w m m

N N N m r- W

N N 3

2

Ln

t- 3

z'

W 3 3 r- W

2

0 N

W m

z'

E x E X E r n X

m m 3 N n m

w m o N N n r N

732

3 3 3 w w w w w w

m m m m t- L - c - t- w w w w

0 N I

m m t - t - m o

P 3

m 0 t-

W

N m

f'

E

X X X X

c o r n m m L- m m W

m m * 0

N W N

b m I

m m

5

I z I1

X V X V II

V V

1

- z? -

3:

Y)

5 4 1T

133

TA

BL

E 6

6.

(con

t.)

-a M

eth

ods

of

rp

N.

It'

R"

R

X

sy

nth

esis

M

.p.

or B

.p.

Ref

eren

ces

Der

iva

tiv

es

W

42

C,H

, H

-c(cH~)=cHc(cH,)=N-

IV a

-XX

II a1

M. 170-172"

261

43

C,H

, H

-C(C

H,

)=C

HC

(CO

OH

)=S

VIII

M. 225-227"

262

~(CH,)=CHC(CONHNH,)=N-

IV a-XXII a1

M. 156-158"

262

-C(CH,)=CHC(CONHNH,)=N-

VIII

M. 194-195"

262

-C(C

H,

)=C

HC

(CO

NH

NH

CO

CH

, )=N-

VIII

262

-C(C

H, )=

CHC

(CO

N-N

)=N

- VlII

M. 215"

262

II

CH

z-OC

C+CH,

Na s

alt

45

C,H

, C

6H

5

-C(C

H,)=

CH

CO

N(

XXVI b

M 69-90"

261

CH3

m m m m 6 6 $ 6

e n

x x x x 51 E E B x x x

735

TA

BL

E 6

8.

Am

inod

ipyr

azol

yls

N.

Com

pou

nd

s M

eth

ods

of

syn

thes

is

M.p

. or

B.p

. R

efer

ence

s D

eriv

ati

ves

1 Ix

M. 1

08"

70

3 *2

CH

,I : 2H

,O :

M.

120"

(d

.)

z z

a m

z"

2 u X" u

W fc t- t-

W W c iD c

n a P a

X X E

Ln w w w W T C .

$ t- t - t - m t-

3 3

7 D P r i e s s 5 5 X x x R r

w w i E E 6

Q D

E xx X

5

t- 0 (D t- t- t- P * (D

0 c- l- 3 3 W r- (D

N t-

D D Q Q D Q e

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(D 00 N m N N

739

W

W

W c - i

Q I

X x

3

m

W 3

6 E;

N c 3 c t- 3

i i

Q Q

& &

3 3

0 r- W

W c 3

f.

Q

Fi x

3

a z

d V

d

8 W

-* 0 N

f'

Q

E

3

m a r

E, z 2'

r

d V

d V

v1

E * m

3

t- W LD l- W

- a

2 N

i 2

- LD N (D

Q Q

s X X x X

5

* 3

t- 0 2 c t-

t- W W

3 3 3

a

m z

am V xm v d

V X" V

X

01 m m m

N N N

0 (D

6 m 3

s

3 0 l- 6 W

3 m 0 m *

i s

n n

% W

8 W

0

W W m (0 z LD l- W

m 4 N

i

X z

u d t? z" u

X" u x- t? u

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d tT u

m

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z z X

X" 0

2" U

r" 0

9

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74 1

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5

P

5 54

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m m (D 01 (D (D

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M

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m s:

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i

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743

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8201

8201

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I

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8&

11

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1

ES6

e PP

L

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T

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06

s

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10

1

GI11

.ZST-OST .W

.L91-S91

'W

81/,061-S81 'ff

.S '901-901 .IN

80 'o/,~or-zor 'a

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91-E91

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.S 'E

91-E91

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8

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H

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P

H

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EH

3

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H

HI

TA

BL

E 7

0.

(con

td.)

Met

hod

s of

N

. R

R

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sy

nth

esis

M

.p. o

r B

.p.

Ref

eren

ces

Der

ivat

ives

13

C,H

, H

O

CO

C,H

, V

f

M. 170-171"

1028

XX

VI

a 1028

C

1028

14

CH

, C

H3

OC

H,

Ig

M

. 85"

101

15

CH

, C

H3

OC

2H5

Ig

M. 93

"; 98"

101,1058

16

C

H,

CH

,CH

, O

CH

3 I

g

M. 106-107"

101

17

CH

, C

H,C

H,

0C2H

5 Ig

M. 86"

101

18

CH

, C

H,C

H,C

H,

OC

ZH

.5

Ig

M

80.

5"

101

19

CH

, C

H,C

H,C

N

OC

H,C

H,C

N

**

M. 194-195"

590

20

CH

, -C

(CH

3kC

HC

0C-

XX

VI

a M. 246"

947

77 2

Ben

zoyl

der

iv. :

M. 181"

***

* F

rom

3-m

eth

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acr

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le.

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m 3

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ith

acr

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itri

le.

Fro

m a

ceta

ceti

c ester-isonicotinoylhydrazone b

y h

eati

ng

at 150-160"

**

***

PS

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XX

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s

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H

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1

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W 03

E

cd

i

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=* V

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m

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W 3 L- c-

5: X

W W In m m W

In In N W W W

d d

X m X m

In r(

m w rl O 3 3 3

N 3

7 4

TA

BL

E 7

2.

4-H

ydro

xpyr

azol

es

N.

R

R'

R"

X

M

eth

ods

of

syn

thes

is

1H

2H

3 C

H,

4 C

H,

C6

H5

C6

H5

C6

H5

C6

H5

9 C

fiH!i

10

H

11

H

12

H

H

H

OH

CH

,CH

,CH

(CH

,),

H

H

H

H

H

H

H

OH

OH

OC

OC

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5

OH

H

OC

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H

OC

ON

(CH

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H

OC

ON

HC

6H,

H

OC

OC

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CH

3 O

H

CH

,CH

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H

Cfi

H5

OH

111

b b, d

I11

d

M

XX

VI a

111 b

XX

VI a

XX

VI

a

XXVI a

Ih

Id

Ih

M.p

. or

B.p

.

M.

118-

118.

5"

M.

85"

Oil

M.

89"

M.

119-

120"

B.

335"

/736

Ref

eren

ces

,Der

iva

tiv

es

.HC

l: M

. 14

9-

1060

15

1"; 1

57"

129"

33

6 P

icra

te:

M.

128-

159

1060

1060

1059

456

B.

154-

155"

/0.

3 10

75

M.

168"

10

59

M.

78"

1059

M.

173.

5"

91 1

M.

179-

181"

10

81

M.

188"

91

1

.HC

l: M

. 80"

-HC

l.l/,

PtC

1,:

M.

180"

m m N

m P m 3

I LD

a I

8

s? V

31

VJ

Ew m 3

I m N

I 3 s 2

m m m m m ro N N N

N d

x x x

3 u

W m N m m N m ro N m m m m m m N N N

2 2 2

m

I h i

rl

m N 3 i

m

W 3 s

m o 4 l m m m m - 0 3

I N (D

W m

d

2 2 2 % 2 2

m

I h i

rl

m N 3 i

W 3

I N (D d

4 m 3

% 2 2

x x m 51 x X

W m N m m N

m m N W Ln

N (D m N

(0 m N

W m N

m

I I m 3

N m 4

R

I

m 3 3

3

3

N 3 i

b m i

E2 i

I

a n

‘CI P e3 n x

5 0 u X 8 8 0 0

z V

Ern V

s;” V

97 V

a -

z u

m 3 3

2

d

5 @

X* V

8

Xrn u

X

m m N (D m N

0 m

I m

t- m d

3

OD N 3

s 2

cd

P 5 E 3

u

8 8

X X

c m

n m

N m i

m

2 i 3

W t- d

I Ln

t- 3

T: 0 m 3

i

z? u

m

2 uq m m

m

r" V

X

4 m

0"

L n w m m co m t-

m

753

TA

BL

E 7

2 (c

on

td.)

4-H

yd

rox

yp

yra

zole

s n

ot

com

pri

sed

in

the

pre

ced

ing

tab

le

4

cn

sr

N.

Co

mp

ou

nd

s M

eth

od

s of

sy

nth

esis

M

.p.

or

73.p

. R

efer

ence

s D

eriv

ativ

es

la

M

17

5"

17

8

VII

I M

. 98-

99"

42

3

3

HSC

v c2

M

. 71

-72"

V ~

2-V

I b

42

3

TA

BL

E 7

3.

5-A

lkox

y-

and

acyloxy-pyrazoles

N.

H

R'

R"

X

M

eth

ods

of

syn

thes

is

M.p

. or

B.p

. R

efer

ence

s D

eriv

ati

ves

1

CH

,CH

,OC

H,C

H,

2 C

H,C

H,C

H,

3 C

H(C

H,)

,

4 C

H,C

H=

CH

,

5 C

H,(

CH

,),C

H,

6 C

H,C

H(C

H,)

,

I C

H,(

CH

,),C

H,

8

CH

,CH

,CH

(CH

,),

9 C

6H5

10

C,H

,

11

C6H

S

12

C

,H,

13

CH

,

14

C

H,

15

C

H,

16

CH

, V

I V

I

H

H

C"3

H

H

H

H

H

OC

ON

(CH

,),

OC

ON

(CH

,),

OC

ON

(CH

.J,

OC

ON

(CH

,),

OC

ON

(CH

,),

OC

ON

(CH

, ),

OC

ON

(CH

,),

OC

ON

(CH

,),

OC

H,C

H,

OC

OO

C ,H

,

XX

VI

a

XX

VI

a

XXVI a

XX

VI a

1138

B.

110"

/0.6

11

38

B.

10

5"

/0.0

4

1138

B.

10

8"

/0.1

11

38

R. 1

10

"/0

.05

11

38

B.

11

3"

/0.1

2

11

38

,11

18

B.

115"

/0. 2

11

38

B.

11

2"

/0.2

11

38

M.

34-3

5"

1023

.H

CI.

'/2P

tC1,

:

M.

141-

143"

B.

14

8"/

0.

5 11

38

5. 1

48-1

50"

/0.

06

1075

M.

167"

31

4

5. 1

02"

/0. 6

11

38

1138

M.

196-

198"

11

26

1126

TABLE 7

3. (c

ontd

.)

-a

Met

hod

s of

N

. R

R

' R

X

sy

nth

esis

M

.p.

or B

.P.

Ref

eren

ces

Der

iva

tiv

es

11

CH

,CH

,

18

CH

,CH

,F

19

CH

,CH

,0C

H3

20

CH

,CH

,OC

,H,

21

CH

,CH

,

22

CH

,CH

,CH

,

23

CH

(CH

3)2

24

CH

,CH

=CH

,

25

CH

,(CH

,),C

H,

/CH

:, 26

-C

H \CH

,CH

:,

27

CH

,CH

(CH

,),

28

C(C

H,)

,

29

CH

,CH

=CH

CH

,

,CH

=CH

,

\CH

:, 30

-C

H

31

CH

,(C

H,)

~C

H,

32

CH

,CH

,CH

(CH

,),

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

OC

ON

(CH

,),

OC

ON

(CH

,),

OC

ON

(CH

, ),

OC

ON

(CH

, ),

OC

ON

(CH

,),

OC

ON

(CH

,),

OC

ON

(CH

,),

OC

ON

(CH

,),

OC

ON

(CH

,),

1127

et

hy

len

egly

cola

ceta

l M

. 180-1

82"

VII

I

XX

VIa

B

. 11

5-11

8"/0

.5

1O75

.111

4

B.

103"

/0. 2

11

38

1138

1117

,113

8

1138

B.

116"

/0. 3

11

38

B.

124"

/0.

3 XX

VI a

XXVI a

B

. 10

?"/0

. 15

1120

,113

8

B.1

11

"/0

.2

1138

B.

106"

/0. 3

5 11

38

B.

l08"

/0.

2 11

38

B.

124"

/0.4

11

38

B.

100"

/0. 2

2 11

38

1138

XX

VI

a B

. 10

5-10

6"/0

.18

1118

B.

118"

/0.1

8 11

38

XXVI

a

B.

131"

/0. 5

11

13,1

138

33

CH

,(C

H,)

,CH

,

34

CH

,(C

H,)

,CH

,

/CH

,CH

, 35

-C-(

CH

,),C

H,

\CH

~O

H

/CH

,-CH

, 36

-CH

)C

H,

\CH

,-CH

,

37

CH

,C,H

,

38

-,

:H

2e

%

-

39

C,H

,

H

H

OC

ON

(CH

, ),

OC

ON

(CH

,),

1138

B. 140"/0.2

1138

OC

ON

(CH

,),

H

1138

OC

ON

(CH

,),

XX

VI

a

B. 165-168"/0. 15

1075

OC

ON

(CH

,),

OC

OC

,H,

OC

H,

XX

VI

a B. 150"/0.3

lM5,

1119,1138

XX

Vl

a

M. 119"

493

B. 277-282"/125

555

.HC

l.'/,P

tCl,

H,O

: D

ec.

180-182"

476

826

400, 555, 785,

-HC

1-'/,

PtC

1,

:

979,1087

M.

180"

; 195"

476

555,1086,1089 .H,O: M. 62-63"

981,1090 a

981

981

47 6

476

732,1075,

1112

VII

I

XX

VI

a

1%

VIE

XX

VI

a

VLU

VII

I

XX

VI

a

XX

VI

a

XX

VI

a

XX

VI

a

B. 239-240"/212

B. l8O"/lO

M. 38. 5-40"

H.300-302"/752

M. 53-54"

M. 158"

M.

78"

M. 47"

M. 52"

M. 28

"

M. 50

"

40

C,H

, H

41

C,H

,

42

C,H

,

H

H

OC

H,C

H,O

H

OC

H,C

OO

H

OC

H,C

OO

CH

3

OC

H,C

OO

C,H

,

OC

OO

CH

,

OC

OO

C,H

,

OC

ON

(CH

,),

43

CsH

s

44

C,H

5

45

C,H

,

H

H

H

B. 167-172"/2-3

B. 160-16%"/0. 2

B. 151-153"/0. 3

-4

01

-4

46

C,H

, 1075

H O

CO

N(C

,H,)

, X

XV

I a

TA

BL

E 7

3. (

con

td.)

2 N

. R

R'

R"

X

m

47

48

49

50

51

52

53

54

55

56

57

58

59

60

61

'tjH

5

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

OC

ON

(CH

,CH

:CH

, ),

OC

ON

[CH

,(C

H,)

,CH

~I,

OC

ON

HC

,H5

OC

OC

H,

OC

OC

H,C

l

OC

OC

H,C

H,C

H3

OC

OC

,H,

OSO

,C,H

,

OP

S(0

C ,H

1,

OC

ZH

5

OC

OC

H,

OC

OC

,H,

XXVI a

XXVI a

XXVI f

XX

VI a

XXVI a

IX

XXVI a

XX

VI a

XXVI a

XXVI a

VIE

Ig

XXVI a

XXVI a

XXVI a

VLU

--__

~ ~~

Met

hod

s of

sy

nth

esis

M

.p. o

r B

.P.

Ref

eren

ces

Der

iva

tiv

es

-

R.

160-

162"

/0.

4

B.

170-

171"

/0.

2

M. 9

2-93

"

B.

20

0"/

10

M.

143-

145"

8. 1

72"/

8

M.

75

-76

"

M. 9

1-92

"

B.

125-

126"

/0.1

M.

195"

M

84"

B.

173-

175"

/0.

2

M.

76"

M.

192-

193"

1121

1075

1048

476

1109

679

574

47

6,7

85

476

953

139

98

0

98

0

1075

98

1

10

74

,11

25

a

1074

m m

N

0 3 E - t -

759

TABLE 73. (c

ontd

.)

Met

hods

of

syn

thes

is

M.p

. or

B.p

. R

efer

ence

s D

eriv

ativ

es

R'

R"

X

-3 0

m

N.

R

72

JJcl

O

CO

N(C

H:,I

,

OC

ON

(CH

,),

XX

VI

a B. 163-165"/0.1

1075

H

H

XX

VI

a M

. 140-141"

1075

l4 9,,,,

1125 a

K s

alt

O

CO

C,H

, X

XV

I a

Cl -Q

SO

*Cl

M. 137-139"

1074

VII

l

OC

ON

(CH

,),

OC

ON

(CH

~;,

OC

OO

C,H

,

XX

VI

a

XX

VI

a

B. 143"/0. 1

1075,1138

B. 205-207"/0. 2

1075

75

C,H

,

76

C6H

,

CH

,CH

, H

C6

H5

H

H

77 a

XX

VI

a M

. 196-198"

1074,1125 a

M. 8

0"

1074

VII

l M

. 184-185. 5

" 1074,1125 a

E

thyl

eneg

lyco

lace

tal

1127

P

olyv

inyl

acet

al

H

H

XX

VI

a

XX

VI

a

M. 113-114"

1000

Su

lfon

e: M

. 140

M. 7

1"

313

78

79

C6

H5

O

CO

C,H

,

OC

ON

(CH

,),

'sH

5

OC

ON

(CH

,),

XX

VI

a

M. 103"

313

Su

lfon

e: M

. 156"

m n L D M

LD

0

(D N * d

t- m * I

LD m d

2

t- t- d

LD t- 3

I

n n n d n d m

31- s U 0 u

3: 3: 3: 31

3 * N . 7 m m m m LD m (0 m m t- m m

761

0 P U

8 3

0" 0

z

r" d d u u u g d z d 0 u u u

762

CH

3 O

C,H

, vi

n M. 75"

1097

CH

3 O

CO

CH

, X

XV

I a

M. 167-168"

1097

XX

VI

a-V

III

100

C,H

,

101

C,H

,

102

C,H

5

XX

VI a

M 117"

978

XX

VI a

M. 139-140"

66,964

IV b

-XX

VI a

M. 236"

432

XX

VI a

103

C,H

, X

XV

I a

M. 178"

843

.HC

1: M. 140"

843

fJ""

104

C,H

, X

XV

l a

M. 171"

843

XX

VI a

M. 138"

587

106

C,H

,

107

C,H

,

108

C,H

,

4

01 0

XX

VI a

M. 132"

947

XX

V i

-XX

VI a M. 226-221"

1070

M. 227"

161

**

* F

rom

l-p

heny

l-3,

4-di

meth

ylpy

razo

l-5-

one w

ith

m-n

itro

ben

zald

ehyd

e in p

rese

nce

of

HC

1.

Fro

m l-p

heny

l-3-

meth

ylpy

razo

l-5-

one

wit

h b

enza

ldeh

yde

and

0-n

aph

thyl

dm

ine,

or

ben

zal-

0-n

dp

hth

ylam

ine.

**

X

3 3

3 0

.L c

c

r

d V

0 - 3

164

11

5

C,H

,

116

C,H

,

117

C,H

,

118

C,H

,

1029

t tt

M

. 14

7"

1029

M.

15

8"(

d.)

tl

M

lS

l"(d

.)

1029

1029

M

. 1

51

'(d

.)

tt

119

C6H

5 '6"5

a,,,

~ t

t

M

134"

(d.)

10

29

+ * *

Fro

m 1

-hro

mo

-3,

4-d

imet

hy

lpy

razo

l-5

-on

e w

ith

NaO

H.

I*** F

rom

3,4

-dim

eth

ylp

yra

zole

wit

h N

aOB

r o

r fr

om

l-bromo-3,4-dirnethylpyrazol-5-one w

ith

NaO

H.

t F

rom

l-p

heny

l-3-

methyl-4-hromopyrazol-5-one in

eth

yl

alco

ho

l, i

n p

rese

nce

of

Na

acet

ate,

ace

tic

acid

an

d C

uS

04

; als

o i

n p

rese

nce

of

py

razo

le b

lue.

t t

F

rom

py

razo

le b

lue

and

the

corr

esp

on

din

g l-a

ryl-

3-me

thyl

-4-bron1opyrazol-5-one, in

pre

sen

ce o

f Na a

ceta

te a

nd

CuS

O,.

NR

R

' R

M

eth

od

s of

sy

nth

esis

M

.p. o

r B

.p.

Ref

cren

ces

Der

ivat

ives

12

0 -(

==

=..

12

1

H&

M.

164"

(d.

1 10

29

M. 1

62. 5

-163

. 5"

10

30

It

* F

rom

1,o

- tolyl-3-methyl-4-bromopyrazol-5-one

and

bis

-p-b

rom

oph

enyl

pyr

azol

e b

lue

in p

rese

nce

of

NaO

H a

nd C

nSO

,. * *

Fro

m 1

, o (

or p)-tolyl-3-methyl-4-bromopyrazol-5-one in a

ceti

c an

hy

dri

de,

in p

rese

nce

of

acet

ic a

cid

, Na-

acet

ate

and

CuS

O,.

m

u1

4

m

m

TABLE 74.

Po

l y h

yd

r oxy

p yra

zole

s

d

Met

hods

of

N.

R

R'

R"

R"'

syn

thes

is

M.p

. or

B.p

. R

efer

ence

s D

eriv

ativ

es

'CiH

5 O

CO

C,H

5 H

O

CO

C,H

, X

XV

Ia

M. 111"

682

2 O

CO

C,H

, H

O

CO

C,H

, X

XV

Ia

M. 133"

43

C6

H5

O

CO

C,H

, C

H,C

H,

OC

OC

,H,

XX

VIa

M

. 120"

711

C6

H5

O

SO,C

,H,

CH

,CH

, O

SO,C

,H,

XX

VI

a

M. 189"

711

m c- N

LD m LD * *

i i

3 N

Ld

E

m t-

* T?

m

Lo-

d

767

TA

BL

E 7

6.

Hy

dro

xy

py

razo

les:

py

razo

liu

m s

alt

s

Met

ho

ds

of

N.

R

R'

R"

R"'

R""

X-

syn

thes

is

M.p

. o

r B

.p.

1

CH

, C

H,

H

OH

H

1

IV a

-c

M.

141"

c1. S

;PtC

l,

M. 2

12"

(d.)

3 C

fiHs

H

OH

n O

H

H

OH

OC

H,

H

CH

3 H

M

195"

(d.

) I

IV c

c1

Dee

. 20

3"

Cl.'

/,PtC

l, M

. 19

3" (

d.)

OH

M

. 13

2-13

5"

OH

I c1

C1.

'/2Pt

Cl,

I I I I 1.1,

IV c

M.

150-

155"

(d

.)

M.

201-

202"

M.

225"

(d

.)

M.

190-

195"

(d

.)

IV c

M

. 19

6-19

7"

(d.)

M.

198"

(d.

) IV

c

1v c

11

1.19

8"

IV c

M

. 13

0"

XX

VI

a

M.

132-

133"

Ref

eren

ces

10

60

255

255

255

255

654

5 57

557

972

W l- a t-

Ln v)

a - 2 3 I "

m w 3 Q ) i d

z ' z '

u z ,

X rn X 31 X

tT z? u

m X u

i 3 0 m 3 m

769

L- cp 3 3

i

0

2 W

I N W

a

P

6

m

B M

X

X

Ern V

3

c- f 3

m m I m m

2

P

E

m G M

m

X

n Xw V

m

t- f 3

& W

I m m

2

P

6

m B M

6

X

t7 cp

In 0 3 3

h

a v

LD m s:

a

6

m m V

X

LD

E 0 ?I

7-70

Ln

0 3 3

P

Ln

0 3 3

W

5 2

P

ti x

0" 0" I I

m a

N i ,+ 3

0 W Ln

id I

3 3

711

4

4

Lv

TA

BL

E 7

8.

N-u

nsu

bst

itu

ted

3-

or

5-th

iop

yraz

o1.e

~

Ru

x

R'

/I

Met

hod

s of

Der

iva

tiv

es

N.

R

R'

x sy

nth

esis

M

.p. o

r B

.p.

Ref

eren

ces

1H

H

SC

HZ

CG

H,

I11

c 91

3 P

icra

te:

M. 11

0-11

1"

2H

C

H3

SCH

, III

c

3H

C

H,

SCH

,CH

3 I11

c

4H

C

H,

SCH

,CH

,CO

OH

I11

c:

913

Pic

rate

913

Pic

rate

913

Pic

rate

M. 1

64-1

65"

M. 1

32-1

33"

M.

134-

135"

Pic

rate

:M.

145-

145.

5"

5

H

CH

3 SC

H,C

GH

, I11

c 91

3

6 C

,H,

C,H

, SC

H,

Xe

M

. 16

0"

162

Ace

tyld

eriv

: M

171"

SO,C

H,

g M

. 25

0"

162

TA

BL

E 7

9.

3-T

hio

pyr

azol

es

N.

-. 1 2 3 4 5 6

R

R'

R

X

Met

hod

s of

sy

nth

esis

M

.p. o

r B

.p.

Ref

eren

ces

Der

ivat

ives

C6H

5 C

H,C

H,

CH

,

SCH

,

SO,C

H,

SCH

,

SO,C

H,

SCH

,

SO,C

H,

SCH

,

SO,C

H,

SCH

,

SCH

,

B. 327"

B. 175"/10

M. 105"

M. 62"

M. 121"

B. 135"/32

M. 122"

B. 151"/31

M. 85"

M. 40"

B. 205-208"/20

B. 160-165"/12

~ ~

~ ~~

~~~

655

.HC

1: M. 132"

655

.HC

1.l/,

PtC

1,.H

,O

: M

. 130

" (d

.)

655

913

720

720

720

656

656

656

656

684

684

p:

i 3 N

7 7 4

R m

I d m 3

3 * 3

I 0 -

3

s z

m 0 0 4 9 m

m m m" 0 0- 0 F- m m 6 fs m ffi N O 3 3 m m 3 - N 3 4 % 2 0 N m d

9 V

V d g zw

d u d d U O

d U

r: > *

m

m- m m

rr W

r r r r w W ' W w

w w m m m cc w w w

0 ( 0 3 t - - 4

2 2 r w 0 o w m i

I I w m 2- o w m + m

3

rr 3

n o j c j

m* 0

m

m

2 V

m m m e r r cy w w w

m

m

Z W V

m

776

C6

H5

C

H3

H

SCH

(CH

,),

M

B. 3

09-3

10"

64

9

B.

176"

/16

M. 8

3"

649

M.

56-5

7"

649

B. 1

84-1

88"

/11

B.

313-

314"

64

9

B. 1

68-1

75"

/9

B.

246"

/20

649

M. 9

2"

649

M. 9

3"

70

0,7

01

701

Oil

70

1

Oil

70

1

SO,C

H(C

H,)

,

SCH

,CH

=CH

,

g

XX

Vl

d

' C

6H

5

H

C6

H5

H

M

C6

H5

H

SC

H,C

6H,

S0,

CH

,C6H

,

SCO

C6H

, 10

C

6H5

H

11

C6H

5

12

C6H

5

H

H

"O2

6 H

S

-S-S

yJC

H3

I C,H5

SCH

,

SO,C

H,

SCH

,

SO,C

H,

SCH

,

M

M.

61"

M.

160"

67 1

14 AN''

M. 84"

67

0

670

M. 1

35-1

36"

64

9

M. 1

39"

672

M. 15

4"

67 2

M. 1

32"

67 2

.HC

1: M

. 18

5"

.HC

1: M

. 221

"

S0,

CH

3

SCH

, H

W W 9 9 9 % 9 s 3 L o w w w w (D t-

N 3 3 3 3 L D W t- N N N N w w w t - P t - t - w w

P 3 m m 3

3 E X I N I 2 1 3 N N N 0

778

I I

l l 'e:

e:

i

;6" x

s m

D I c u m m m

N

A N

x x :I

TABLE 8

3.

Th

iop

yraz

oles

not

co

mp

rise

d in

th

e p

rece

din

g ta

ble

s

-

4

0

Met

hod

s of

m

N.

Com

pou

nd

s sy

nth

esis

M

.p. o

r B

.p.

Ref

eren

ces

Der

iva

tiv

es

1 2 3 4

I I

C6

H5

C

GH

S

* **

Ix

IV c

IV c

M. 12

4"

M. 14

9"

M. 19

8"

665

665

703

703

M 1

98

M. 23

4"

665

703

XX

Vl a

M. 1

34"

70

3

XX

VI

a B

. 72

-76

"/2

10

78

* F

rom

1 -ph

enyl

-3-methyl-4-bromo-5-benzoylthiopyrazole b

y h

eati

ng

at 1

50"w

ith

HC

1.

** F

rom

bis

-[ t-pheny1-3-methylpyrazolyl-(5)~-disulfide by

vac

uu

m d

isti

llat

ion

.

2 m e r x x e m T m m m

782

W W W

cu 3 >

a

3

W 3

E

mm % M

m

mm u

m

3 cu

w w w m W c o co co w w w w

m 3

g s a a

m m

m

xQ mm u u

784

m

v1

* d

.d $

.-(

N

I n" . I

m d

N

b !a a c r(

rn

W m W ;I a E

m m m m w w

0 CO 3

s

cd

0 5 e N

U

mi u

m

Em v m

mm u

m: u

,-I

(D W -F W (D

m

cu m 4

m 0 N

cd cd

E E U

mm ON

v m cn

m

mm u mm u

Em u mm u

e- co

785

W W

W W m m

d

4 Q I

m m

z? 0

z? u

a

u

0 3

d

0 r 0 m m

/

3

786

‘ I I

4 m

4 h

z

p:

rd n

X

s N 3 I n N 3

Zi

rd w

X z? V

% W

A a, m

A

0 t- m 0 L- m

v 3 3

m v N

f A

787

TA

BL

E 8

8.

Pyr

azol

e T

hio

, Su

lfon

ic, a

nd

Ph

osp

hon

ic A

cid

s an

d t

hei

r F

un

ctio

nal

Der

ivat

ives

Met

hod

s of

N

. R

R

' R

" R

'"

syn

thes

is

M.p

. or

B.p

. R

efer

ence

s D

eriv

ativ

es

TA

BL

E 8

8.

(con

td.)

Met

hod

s of

-4

m

OD

N.

R

R'

R"

R"'

sy

nth

esis

M

.p. o

r B

.p.

Ref

eren

ces

Der

iva

tiv

es

4 C

SSH

C

H,

H

'GH

5 24

0

5H

6H

7 C

6H5

H

H

H

CH

,

CH

, H

9H

10

H

11

H

H

SO3 H

CH

, SO

,H

CH

, SO

,H

S0,

CI

SO,H

V

I a-

VII

I M

. 25

7"

889

Pyr

idin

e sa

lt:

SO,N

(C,H

,),

VI

a M

11

2-11

3"

M.

169-

170"

889

M.

275"

88

9

SO,N

(C,H

, ),

VI

a M. 1

27"

889

SO,H

X

XI

h M

. 235

" 7

01

N

a sa

lt

Ba

sa

lt

SO,H

V

I a-

VII

I

S0,

CI

VII

I M

. 10

1"

70

1

SO,N

H,

VII

I M

. 243

" 7

01

SO,N

HC

,H,

VII

I M

. 127

" 7

01

SO,H

X

XI

h

M. 2

46"

685

Ba

sa

lt

S0

,Cl

VII

I M

. 77"

68

5

SO,N

H,

M.

227"

68

5

so,N

HcG

FII

j M

. 11

8"

685

H

XM

e

M. 3

45"

(d.)

88

9

H

XM

e

M. 2

57-2

58"

548

Ba

sa

lt

CH

3 X

M e

73

9 .1,

5.H

,O:

M. 2

87-2

88"

Ba

sa

lt

VII

I M

. 98-

100

" 73

9

XM

e

449

N l?

I

L- 3

2

m d d Ln

d d a a a m o m N N N N m 51 1 3 3 3 + *

< V

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.- M

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1 0

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t-

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d :

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c

LD

xu V

X

r" u

W m W

co t- N

2

* n +

0" rn

X- U

X

m X V

N m *

W W m

a v

t- N N

2

3 u

>

$

X

6r

z? V

Ern u

3

7 90

m 0 t- N 3 3 m m m t- @a N v w * w t- t- w w w

0 t- W w n n r o i

w w ( D w (0 w m a a w e m t-

3

N m

9

x 3 1

c o t - 00 m o d N 3 - i

N n v u5

791

TA

BL

E 8

9.

(con

td.)

-1

a

h)

Met

hod

s of

X-

syn

thes

is

M.p

. or

B.p

. R

efer

ence

s D

eriv

ati

ves

N.

R

R'

R"

R

"'

13

C,H

, C

H3

CH

3 H

S

eO,

XX

I h

64

6 .H

,O:

Dec

170

"

c) D

ipyr

azol

yls

N.

Com

pou

nd

s M

eth

ods

of

syn

thes

is

M.p

. or

B.p

. R

efer

ence

s D

eriv

ati

ves

XX

l h

703

a" 3 E

: a,

0 a 0 u 0

.d

h 0 N cd k

+

a" 0

W IJ

Q,

a s

cd v (D co

cd (D W m

In cv W

e

5! ti

7 93

0 * (D m * W

F m N

2

W v

Q B

0 3 Lo N

W W

B E

X X

N m * LD

794

d t- o v) 0 t-

5 B 2 s

N

& 0 N N

P P

B B

W o t-

U x R

h W o W

0 t- W o t-

U U U

X B fi R

X

m

??

W t- m

795

r * 0

3

3 0

g

d

5

m

XW V

I

X

X

n

3

r N

I (0 N

3

9

N Lo i

i

d .- I I

X

X

n

Ew 3

z

X

N

796

P N n

id w

X

n

N d P N * t- f i

N

t- v) N

v) In N

N v) N

3 In N

I I - N m

i i i

P P

d 3 1 ) X ?rj 8

P i 0

d W m m

P

* m

2" 0

2" 0

Ern U

Xrn u

Xrn $ U tT U $

X m X X

* In (0 t-

$ U

X" U

X

W

Ln N N

P

d m

3 * N 3 LD N

s i

Ln

% U

d U

X" U U =-% i

i z m z

Y' ur U

T r n E El

Fr 0

m 3 *

797

G m

798

0 '

5 N I

N LD N m i%

X m m

g U m" g

x m N N N r( N

799

800

QO z

I1 1

Ln W 0

i v N

id M

X- U

d U

x? U

Xi U

m

9 U

Lo W 0

f Xrn U @ - $

0 I,

41

C

6H,

CH

3 C

6H

5

42

C6H

, C

H3

C6

H5

43

C6

HS

C

H3

'SH5

44

C,H

, C

H3

C6

H3

45

C6H

5

46

C,H

,

47

C6H

, C

6H

S

C6

H5

d')

4-a

zop

yraz

oles

wit

h u

nas

sign

ed s

tru

ctu

re

N=N

CsH

5

V b

3

la

XW

I b

l

XX

VII

a

V b

3

la

M

158-

159"

78

2

M. 13

1"

365

M. 24

7"

895

M. 2

11"

910

M. 16

9-17

0"

782

M. 22

7-22

9"

365

la

M. 15

6-15

7"

164

322

1

Met

hods

of

N.

R

R'

R

X

syn

thes

is

M.p

. o

r B

.p.

ReI

eren

ces

Der

ivat

ives

m 0

c

la

M

. 166

-167

" 22

5 'SH5

CH

3 C,HS

.

a

i l

v P-" 1:

i I - N

802

TA

BL

E 9

2.

Hy

dra

zin

op

yra

zole

s

N.

R

R'

R

X M

eth

od

s of

sy

nth

esis

M

.p. o

r B

. p.

Ref

eren

ces

Der

ivat

ives

1H

2H

3H

CH

, C

H,

CH

, C

H,

CH

, C

H,

C6

HS

H

C

H(O

H)C

H,O

H

H

-CH

(O

H X

HO

H

I 5

C6H

S

HO

CH

,

m

CH

(OH

)CH

,OH

0 0

/C*C

H:,

-NH

N=C

X

M d

\C

OO

C,H

,

-NH

N=

C(C

GC

H,)

, X

IX d

,CS

CH

3

--NH

N=C

, X

M d

C

%C

,H,

NH

NH

C,H

, I

j

NH

NH

C,H

, I

j

NH

NH

C,H

5

M. 157"

7 3

9

M. 184" (

d.)

7 39

M.

169-

170"

7

39

Fro

m L

-ara

-

bin

ose

:M

. 18

1-18

2"

334

Fro

m D

-xy

lose

:

M.

179-

180"

Fro

m D

-glu

cose

33

4 A

cety

l de

riv.

: M. 17

0"

Ben

zoy

l de

riv.

: M

. 16

0"

Fro

m D

-gal

acto

se

Ace

ton

e de

riv.

: M

. 16

8"

Ace

tyl

deri

v.:

M.

177"

Fro

m l

acto

se

334

Ace

tyl

der

iv:

M.

195-

96"

Fro

m c

ello

bio

se :

M.

245"

(d

.)

Fro

m L

-ara

bin

ose

:

334

M.

177-

178"

Fro

m D

-xy

lose

: M

. 18

8-18

9"

Ace

tyl

der

iv:

M.

180-

198"

P --2 3

c n n P m 0 e m m W

LD LD s c

h

4 :: i s

(0 Y) 3

N

U U

H H

r"

d rn 31 U

d d u d U

Y) Y)

U 4 3 d m 3 N 3 3 3

M

805

TA

BL

E 93

(con

td.)

N.

R

R'

R"

X

Met

hod

s of

sy

nth

esis

M

.p.o

r B

.p.

Ref

eren

ces

Der

iva

tiv

es

3 C

,H,

CH

, C

H,C

H,

-N=N

NH

X

IXd

M

. 10

1" (

d.)

736

H5C

z1N

J

CH

3

M.

86"

736

TA

BL

E 9

4.

Met

al P

yra

zole

s

a)

R" 'nR'

y'' I R

N.

R

R'

R"

X

Met

hods

of

syn

thes

is

M.p

. o

r B

.p.

Ref

eren

ces

Der

ivat

ives

C6

H5

H

C6

H5

H

C6

H5

H

CH

3 C

H3

5 C

H3

CH

3

6 C

H3

CH

3

7 C

H,C

H,

CH

,

8 C

H,C

H,

CH

3

9 C

H,C

H,

CH

,

0 4

10

C6H

5 C

H,

H

H

H

CH

3

CH

3

HgC

l

Hg

Br

HgO

CO

CH

,

HgC

1

Hg

Br

-Hg)I

"M.cH

3 I

H3C

hH

3

Hg

oH

HgC

l

Hg

Br

HgC

l

M. 2

26"

380

448

M.

212-

213"

44

8

M.

191"

3

80

448

HgC

1, : M

. 238

"

448

-Hg

Br2

: M.

144"

-l/,H

gBr,

: M

. 20

4"

M. 22

5"

448

M. 22

3"

44 8

448

'HgC

1,:

M.

229-

230"

448

.HgB

r, :

M.

140"

448

.HgC

l, : M

. 17

0"

E- E- L- E- m m

0 Ln

a; 0 N Ln

I e + 0 E- N N

0

s T:

M M

ki i x

3 N m

808

& W 3

n m e W m m

& N 3

I I L- N 3

3 W 3

OD In 3

809

I

3

3 P-

b w

4 0 0 0

I 3 In 3

N v) H

& m

I I I m O P - W o w w

t-

I W

(D (D

I

c' m 3

W m I I

m m m b

5 2 2 4 3

3 3 3 - 3 3 d 4

d d d

W

d d d

9 C

H,

I

VII

I

P

NHNO,

-c\

M.

123"

93

3

M.

158-

159"

94

3

M.

167"

9

34

XM a

94

3

XIXa

M. 1

53-1

55"

93

8

10

C

H,

c1

'ljH

5

CO

OC

H,

XM

a

M. 9

7"

54

.HN

03

-Pic

rate

:

M. 2

24"

I H

R'

X

Met

hod

s sy

nth

esis

M

.p. o

r B

.p.

Ref

eren

ces

Der

iva

tiv

es

1 B

r n

CO

OH

VIII

M.

240"

(d.)

7

68

XV

II a

7

68

XX

V b

506

TABLE 95

(co

ntd

)

m

c.

N

Met

hod

s of

R

' X

sy

nth

esis

M

.p.

or

B.p

. R

efer

ence

s D

eriv

ati

ves

N

. R

21

3 c1

4 B

r

51

6 C

1

I B

r

8 C

H,

9 C

6H5

CO

NH

,

H

CO

OH

CH

3 C

OO

H

Br

Br

C-,H

5

CO

OH

C-,H

5 C

ON

H,

CO

NH

NH

,

CO

N,

CO

OH

CO

OH

CO

OH

CO

OH

CO

OH

XIX

a

XV

II a

-III

b

V d

2

XM

a

V d2

Vf

XM a

VII

I

VII

I

XIX

a

VJII

VlI

I

XVII a

VI

a-X

M a

XM a

XIX

a

v fl

M.

220

M. - 10

" (d

.)

M. 259"

M. 103-104"

M. 256-251"

M. 105-108"

M.

264"

(d

.)

M.

270"

M. 230-231"

Dec

. 125"

M. 237"

M. 258-261"

M. 256-257"

M. 260-261"

M. 223-223.5"

168

139

Ag s

alt

718

60

60

178

60

60,168,887

60, I

18

.HB

r: M

. 188"

168

168

118

118

139

54

59

59

508

389

Ben

zoyl

der

iv :

M. 269-70"

Ag

salt

* * * m c - c - c - w - - w w w m c - t -

8 g g

X G $

TA

BL

E 9

5 (c

ontd

.)

m

A

N.

R

CL

R'

R"

X

Met

hod

s of

sy

nth

esis

M

.p. o

r B

.p.

Ref

eren

ces

Der

iva

tiv

es

CO

OC

H,

vm

M. 8

0-81

.5"

72

C6

H5

/ C

H,

Br

-CH

1

CO

OH

'C

H,

XIX

a M

. 184

" 88

8

VIII

M. 7

8"

888

XM a

M

. 176

-177

"

241

CO

OH

X

Ma

19

9 1

0

C,H

, B

r C

6H5

11

C,H

, c

1

c1

C

OO

H

XM a

M

214"

67

4

12

C6H

, B

r c

1

CO

OH

X

Ea

M

. 222

" 67

4

Met

hod

s of

N

. R

R

' R

" X

sy

nth

esis

M

.p. o

r B

.p.

Ref

eren

ces

Der

iva

tiv

es

'$5

c1

C

H3

CO

OH

CO

Cl

XVII a

M

. 216

" 88

5

VII

I M

. 57"

88

5

CO

OC

,H,

VII

I M

. 93-

94"

88

5

C6

H5

c

1

CO

OH

Co

cl

V b2

M. 2

23-2

24"

32

, 34

9 A

nh

ydri

de : M

. 178

"

XV

II a

M

. 228

-229

"

71

9,8

85

V b

2-V

III

M. 8

5"; 8

7"

349

CH

, c

1

6OO

H

4H

B

r B

r

CO

OC

H,

CO

OC

,H,

CO

NH

,

CO

NH

C6H

,

-CON

HNH c

1

I

CO

OH

CO

OH

VII

I

VII

I

VII

I

VII

I

VII

I

VJl

I

71

9,8

85

M. 7

4"

349

M. 6

8"; 7

4"

349,

885

M.

183"

; 195

" 7

19

,88

5

M.

156"

88

5

M. 2

48"

885

667

VII

I, X

VII

a

M. 2

26"

(d.)

V c

6

M. 2

84"

(d.)

50

6

Met

hod

s of

N

. R

R

' R

" X

sy

nth

esis

M

.p. o

r B

.p.

Ref

eren

ces

Der

ivat

ives

C6

H5

H

c1

C

OO

H

CO

OC

H,

2 C

H,

H

Br

CO

OH

3 C

H,

UI

4 C

H3

cJ43

c1

C

OO

H

CH

3 B

r C

OO

H

XV

II a

-XIX

a

M. 1

85"

858

VII

I M

. 62

" 85

8

XM

a

M. 2

32-2

34"

(d

.)

506

XX

V b

XX

IV a

M

. 225

" 50

4

XIX

a

M. 2

32"

71

Ag

salt

: Dee

. 120

"

TA

BL

E 9

5 (c

ontd

.)

m

c.

m

N.

R

R'

R"

X

Met

hod

s of

sy

nth

esis

M

.p.o

r B

.p.

Ref

eren

ces

Der

ivat

ives

5 C

H,

C6

H5

6 C

H,C

H,

CH

,

7 C

H,C

H,

C6

H5

8 C

H,C

6H5

CH

3

9 C

6H5

CH

3

10

O

Br

C

H,

f) o

ther

s

l3r

CO

OH

Br

CO

OH

Br

CO

OH

Br

CO

OH

Br

CO

OH

Br

CO

OH

XM

a

M.

208"

7

8

XM

a

M.

159"

71

M.

154-

55

" 78

M.

176-

77

" 7

2

.HB

r: M

. 194

"

XM

a

M.

179-

180"

38

6

VII

I M

. 237

"

386

N.

R

R'

R"

R"

~~

~~~

Met

hod

s of

sy

nth

esis

M

.p. o

r B

.p.

Ref

eren

ces

Der

iva

tiv

es

1H

C6

H5

CO

OH

B

r

CO

OH

B

r

CO

OH

C

OO

H

CO

OH

X

VII

a

M. 2

74"

768

XIX

a

768

CC

mH

XVII a

M

. 244

" (

d.)

11

2

XIX

a

112

Br

VII

I-X

M

a M

. 197

-199

" (

d.)

119

NH

,+

salt

: D

ec.

190-

192"

Pb

-sa

lt

W m m 5: m

d *

m

X

4 N

z? V

sc)

817

0 m m

m w m - w w o w m w m N W N W W ~ W P W P m c - c o P P m P P t - t -

0" 2

818

CO

OC

H,

XX

Ia

M. 1

93"

421

4 NO,

ON

02

C

OO

H

VII

I-X

IX

b

M. 1

84-1

85"

82

3

XV

II a

82

3

3 NO,

C6

HS

Ia

42 1

.H

,O:

M. 1

04"

(d.)

5

NO

C6

H5

C

OO

CH

,

c) n

"n

n'

X N'

~~~

~~~~

Met

hod

s of

N

. R

R

' R

" X

sy

nth

esis

M

.p. o

r B

.p.

Ref

eren

ces

Der

ivat

ives

1 C

6HS

NO

, H

C

OO

H

XVII a

M. 165"

422

2 C

H,

CH

, N

O,

CO

OC

,Hs

IVa

-Vm

M

. 72"

76

6

3 0%

C

H3

NO

, C

N

V c

6

M. 1

69"

886

d)

Nit

rop

yraz

olec

arb

oxyl

ic

Aci

ds

Not

Com

pri

sed

in t

he

Pre

ced

ing

Ta

ble

s

N.

Com

pou

nd

s M

eth

ods

of

syn

thes

is

M.p

. or

B.p

. R

efer

ence

s D

eriv

ativ

es

XVII a

M

. 205

" (d

.)

497

K s

alt

: M.

286-

288"

m

1

c.

W

HO

OC

02N

gcooH

TABLE 9

7.

Acy

lpyr

azol

ecar

box

ylic

A

cid

s an

d t

hei

r F

un

ctio

nal

Der

ivat

ives

.

N.

R

R'

X

Met

hod

s of

sy

nth

esis

M

.p. o

r B

.p.

Ref

eren

ces

1H

C

HO

C

OO

H

VIII

M. 2

45"

495

CO

OC

H,

II

a

M.

135"

49

5

2H

3 C

H,

4 C

,H,

6 C

H,

Cm

H,

CO

CH

,

CO

CH

,

CO

CH

,

CO

CH

,CO

CH

,

CO

OH

V

IJI

M.

257-

269"

78

6

XV

II b

81

2

CO

OC

H,

IIC

M

. 11

2-11

2.5"

78

6

CO

OH

I1

d

VIII

CO

OC

H,

IId

CO

OC

,H,

I1 d

CO

OH

CO

OC

,H,

CO

OH

CO

OC

,H,

VII

I

I1 d

IId

VII

I

M.

157-

158"

M. 1

21-1

24"

B. Z

02°/

26

1057

539,

540

540

389,

540

,105

7

M.

208"

10

57

M. 2

14.5

-215

" 38

9

M.

113"

38

9,10

57

M.

222.

5-22

3"

389

M.

121-

123"

20

0

Der

ivat

ives

Oxi

me:

M. 2

41-2

42"

Sem

icar

baz

one :

M. 2

10-2

12"

.H,O

: M

. 23

3-23

5"

Oxi

me : M

. 16

5"

Ph

enyl

hyd

razo

ne :

M. 1

97-1

98"

Sem

icar

baz

one

.4H

20

: M

. 220

-221

"

7 C

H,

8 C

H,

CO

CH

=CH

C,H

,

Cw

6H

5

CO

OH

CO

OH

VIII

VIII

M. 231.5-233"

200

M. 233"

389,1057

M. 239-240"

389

M. 121-121. 5"

389,1057

M. 211-211. 5"

389

M. 128-128. 5"

389

CO

OC

,H,

CO

OH

CO

OC

,H,

IId

IId

I1 d

C6

H5

C

w6

H5

-c

o~

oc

",

-

10

CH

, C

OO

H

CO

OC

,H,

VIII

I1 d

M. 220.5-221"

389

M. 216-217" (d.)

584

M 179-180" (d.)

469

11

C6H

5

12

CH

O

CO

OH

II

d

CH

O

CO

OC

,H5

IIa

Bis-diethylacetal

13

CO

OH

CO

OC

,H5

VIII

VI a

M. 281"

316

M. 186. 5"

37 6

-co'

'c

o-

14

CO

OC

,H,

M. 245-241"

(d.)

131

VI a

,OH

,O

H

-coc

= cc

o-

15

-

CO

OC

,H,

VIII

4 69

-CH

,CO

OH

: M. 217-219"

TA

BL

E 9

7 (c

ontd

.)

N.

R

R'

R"

X

1 C

OC

H,

H

CH

3 C

OO

H

CO

OC

H,

CO

OC

,H,

2 C

OC

H,

CH

3 H

C

OO

H

CO

OC

H:,

3 C

OC

H,

CH

3 C

H3

CO

OH

CO

OC

H,

4 C

OC

H,

--C

H2C

H2C

HzC

Hz-

5 C

OC

H,C

l H

6 C

OC

,H,

H

CO

OC

H,

CO

OC

,H,

CO

OC

,H,

CO

OH

CO

OH

Met

hod

s of

sy

nth

esis

M

.p. o

r B

.p.

Ia

M

. 17

3-17

4"

XX

V e

M. 6

7-68

"

B.

141-

143"

/14

XX

V e

M

. 19

8-19

9"

M. 9

8-99

"

B.

134"

/12

XX

V e

M

. 197

-199

"

M. 8

2-8

3.5

"

B. 1

55-1

56"

/14

M. 7

8"; B

. 18

2"/1

8

M. 9

4-95

"

B. 1

82"

/10

XX

V e

M

12

7.5

-12

9.5

"

Ia

M

. 18

0"

Ia

M

. 222

-224

"

Ref

eren

ces

Der

iva

tiv

es

60

58,

60

58,

60

58, 6

0

97

97

58

60

60

X

X" V

'i co

9 2 0 ln

Y V Xi?

w 5 3

N r3 * L-

W r3

3 .3 Y

al c A n

m

823

b w 3

* * 3 3

2 s

d

F F

8 8 8 8

u 8

:$

h

a v

" 0 % $ L m r ( D N 2 N 1 3 3 3

1 N C - m 3 3 2 W I il 3

- a v

N C ? N N

824

3 3

m c o w m m m m m m m m m w m m m m m a m m w m c o m m m m n n n m c o m m m

c - c - w w 1 3 c o n N N

* * * * 3 3 3 3 m 1 *

b m I

4 m

3

m

h

a v

& & h P - 3 3. 3 3 N

0 0 0 D N N w m 3 1 0 w N 3 N

0 0

3

I n 4 1 m m N 3 "oh & & oc- m r N 3 N 3

Ln (0 3

r' 2 2 A S 2 $ A r ' A r' r' r ' r ' A

u3

V u v u

m N m 3 m

0 n c - c o N N N

Ln W N N e N

825

I I

p 2" V

: 8 2 e: v v

$ i 8

I I

2 3 N m

4. m k

2

x

b:

m m r - m m

m m

I zm ZT v v

826

4 5 6 7 8 9 10

11

12

13

CH

,

CH

,

CH

3

C6

H5

CO

CH

,

CO

OH

CO

CH

,

H

CO

C,H

,

CO

C6H

,

CO

CH

,CO

CH

,

--C

OC

H=C

H

I C6H

5

I -C

OC

H,C

O

C6

H5

CO

C,H

5

CO

CH

,

CO

C,H

,

CO

OH

CO

OC

,H,

CO

OC

H,

CO

OH

'OO

CZ

H5

CO

OH

CO

OC

,H,

C6H

S

H

CQ

CH

, C

6H5

CO

OH

CO

OH

CO

OC

H,

CO

OC

,H5

CO

OH

CO

OC

,H,

CO

OC

H,

CO

OH

CO

OH

CO

OC

H,

CO

OC

H,

CO

OH

CO

OC

H,

CO

OH

CO

OC

H,

VIE

VIII

VIII

VIII

M. 179-180"

200

M. 267-268"

200

M. 177-178"

2 00

M. 109"

200

VII

I M.

IV a

81 -182"

VII

a

M. 01"

XV

II a

M. 220" (

d.)

VIII

M. 176" (

d.)

VII a

M. 158-159"

M. 84.5-85"

VII

I M. 199-200"

VII

a

M. 129-130"

VIII

M. 185-190"

(d.)

VII a

M. 136-138"

389

389

425

1057

413

p-N

itro

ph

enyl

- h

ydra

zon

e :

M. 258-261"

61

810

810

413

413

TA

BL

E 9

7 (c

ontd

.)

OD

N

m

R'

R

N.

R

R'

R"

X

Met

hod

s of

syn

thes

is

Mp

. or

B.p

. R

efer

ence

s D

eriv

ati

ves

1 C

OC

H,

C6H

5 H

2 C

OC

H,

H

'CjH

5

3 C

OC

H,

-CH

2CH

2CH

2-

4 -c

:b

-

H

H

5 C

OC

H,

CO

OH

H

6 C

H,

CH

3 C

O-C

H,

7 C

H,C

H,

CH

3 C

OC

H,

CO

OH

CO

OC

H,,

co

oc

2H

5

CO

OC

,H,

CO

OH

CO

OH

CO

OH

CO

OC

H,

CO

OC

,H,

CO

OH

CO

OC

,H,

XX

V e

XX

V e

XX

V e

XX

V e

VII

I

VII

I

IV a

VII

I

IV a

M.

162.

5-16

4.

5"

M.

12

9.5

-13

0.5

"

M.

109-

110"

M. 6

7. 5

"

M.

195-

196"

M.

169"

M.

189-

191"

M. 1

10-I

IP

M. 8

5-86

"

M. 1

67-1

68"

M. 5

7- 5

8"

58

61

67

86

58

409

54

0,3

79

379

540

540

540

10

.d ?2

B

C

c .3

m a,

a, w

d

4 m 8

4

N m m W d m m m m

0 a t- 0 N ln

3 m m m

3

3

3 3 n

fe m 3

*a

0

!+ 0

il 0

X Y

3 N m * v)

829

f) A

cylp

yraz

olec

arb

oxyl

ic a

cid

s n

ot c

omp

rise

d in

th

e p

rece

din

g ta

ble

s

N.

Com

pou

nd

s M

eth

ods

of sy

nth

esis

TA

BL

E 9

8.

Am

ino

py

razo

leca

rbo

xy

lic

Aci

ds

and

thei

r F

un

ctio

nal

Der

ivat

ives

N.'

R

R'

R"

R"'

Met

ho

ds

of sy

nth

esis

CO

NH

,

CO

NH

,

H

H

H

H

CH

3

NH

,

FN

C6H

, o

r C

H,

-N

=n

NO

*

CH

3 o

r C

,H,

w

CO

OH

NH,

H

CO

ON

H,

CO

OH

N

H,

XX

II a

XX

II a

VII

I-II

I b

XW

I b

XX

III

b

XX

III

b

XX

III

b

XW

I b

* XX

VI

b-V

IU

**

-

* B

y d

rop

pin

g a

mix

ture

of

dia

zoac

etic

est

er a

nd

cy

anac

etic

est

er i

n a

so

luti

on

of

NaO

C2H

,. * *

Frn

m e

thy

l cy

clo

pg

nta

no

neo

xal

ate

wit

h h

yd

razi

ne

hy

dra

te.

Ref

eren

ces

Der

ivat

ives

M

.p.

or

B.p

.

M.

227"

91

0

M. 23

5"

910

M.

212.

5"

(d.)

15

9 C

u sa

lt

M.

205"

(d

.)

879

M.

181-

182"

87

9

M.

185-

190"

77

8,88

0 .H

Cl:

M.

220"

M.

208"

(d.

) 77

8

M.

209-

211"

77

8

M.

168-

169"

42

1

M.

144"

15

9

M.

227-

228"

92

4

M.

165"

86

TA

BL

E 9

9. Hydroxypyrazolecarboxylic

Aci

ds

and

th

eir

Fu

nct

ion

al D

eriv

ativ

es

I X

N.

R

1 C

H,

2 C

H,

3n

4 C

H,

5 O

CO

N(C

H,)

,

R'

OC

H3

OC

OC

H,

OC

OC

H,

OH

H

b'

I

N.

R

R'

Met

hod

s of

sy

nth

esis

H

CO

NH

, l

a

H

CO

NH

, I

a

XV

UI

c

CH

, C

ON

H,

Ia

CH

,CH

, C

ON

H,

Id

CH

, C

ON

(CH

,),

M.p

. or

B.p

. R

efer

ence

s D

eriv

ativ

es

M.

173"

M 1

82"

M. 1

26"

M. 1

87-1

89"

756

7 56

842

84

2,7

56

1081

1040

X

Met

hod

s of

sy

nth

esis

M

.p. o

r B

.p.

Ref

eren

ces

Der

ivat

ives

1 O

H

H

m

W

2 O

CO

C,H

, n

CO

OH

CO

OH

If

M

. 208

-210

"

1060

111

b-V

III

M. 2

04-2

05"

15

9

If-XXVI

a M. 21

0-21

2" (

d.)

10

60

XX

VI

a 10

60

r m N

t a H

X

N

0 In N

I 0 N N

c

M

.- c.'

m c R n 9 s V

R .+ 3

tj

g u I m

3

R a R

? 3 R

2 B E e 3

F t

L- m 3

I (0 m 3

%

3 : ' X

3 v) N

r v) N

r v) N 0 5: s z

Ln N N N 0 In N

N

v)

* 0 4

x x x x x X 5:

L% N

m

m 3

N .3

3 LD t- m m 2 *

833

c- m N

R v) 3

I L c 3

E'

a c(

v)

9 8 u

X

8

4 U

rn v) N

v) N 3

3:

5: 0 Ln

N N 3 m N

n v) N

d

a I

a E x -a I I

X X X X

z? V

8 8 8 8 f 8

N N - N

0 Ln 3 m N N

0 0 0 0 t - L - m m c - L - m m

t - t - m m N N m m 0 m N N N

" -

L x N

t-- L-- x N

s * m N N

a a 3 3

a a P I CI w

X X X rn X

LD

8 8 8 8 8 :

X

8

X X X

8 8 8

lx N

N OD 3

i

-0 I

EN

s" V

X

8

3 N

m

% N

a I

X

lx N

% * m N N

U U a I * I

* m N lx N

s m (D

i 3 m

s 2

rd

a 3

X m m X X

8 8 8 8

OD W t- m

m

EN

8

m

m

E W V

0 *

TABLE 99

(con

td.)

m

m

w

Met

ho

ds of

N.

R

R'

R"

X

syn

thes

is

M. p

. or

B. p

. R

efer

ence

s D

eriv

ativ

es

3H

COOCH,

OH

COOCH,

II dl

M. 232"

159

xv

336, 337

VII

I 159

c- 2%

COOC,H5

II dl

M. 15

1"

159

m m m m m m 3 3 3 3 3 3 OD m m m a m

m m

t - N O W 3 3 N r l N 3

I , I I I 1 a 3 m m N W rl n L - N o w d 3 3 3 N 3

0 . 0 t - ~ n m h

0" I

TA

BL

E 1

00.

Th

iop

yraz

olec

arb

oxyl

ic A

cid

s an

d th

eir

Fu

nct

ion

al D

eriv

ativ

es

TA

BL

E 1

00 (

cont

d.)

a:

,a 0 N.

R

R'

R"

X

M

eth

ods

of

syn

thes

is

M. p

. o

r B

. p.

Ref

eren

ces

Der

ivat

ives

3H

"Z

H5

4H

SC

H,C

OO

H

5H

SC

HzC

HzC

OO

H

6H

SC

H,C

,H,

I C

H,O

H

SCH

,

8 C

,H,

SCH

,

CO

OC

,H,

CO

OC

,H,

CO

OH

CO

OC

H,

CO

OH

CO

OC

,H,

CO

OH

CO

OC

,H,

9 C

,H,

SO,C

H,

CH

3 C

OO

H

10

C

,H,

CH

, C

OO

H

CO

OC

,H,

I d-111

a

Xe

XV

I

XVI

VIII

Xe

VUI

XV

I

VU

I

XV

I

Xe

IV a

VIII

XV

I

VIII

VII a

M.

128-

129

" 59

9

162

913

M. 9

0-91

" 91

3

M.

222-

223"

91

3

M.

182-

183"

91

3

M. 2

13-2

14"

913

M.

167-

168'

91

3

M. 24

4-24

5"

913

M. 1

26.5

-127

" 91

3

913

M. 1

33-1

35"

913

M. 2

15-2

16"

(d.)

91

3

M.

109-

109.

5"

91

3

913

M.

172-

173"

8

1 5

M.

127-

128"

81

5

-HC

1: M

. 169

-171

"

Ag s

alt

:

M.

227-

228"

.HC

1: M

. 14

3-14

6"

K s

alt

: M

. 217

-218

" (d

.)

K s

alt :

M.

215-

216"

(d

.)

.HC

1: M

. 15

8-16

2"

Ag

salt

K s

alt : M

. 30

1-30

3"

TA

BL

E 1

01.

Azo

py

razo

leca

rbo

xy

lic

Aci

ds

and t

hei

r F

un

ctio

nal

Der

iva

tiv

es

d

N.

R

R'

R"

Met

hod

s of

X

sy

nth

esis

M

.p. o

r B

.p.

Ref

eren

ces

Der

iva

tiv

es

1H

C6

HS

N

=NC

,H,

H

CO

OH

X

VII

a

M.

196-

197"

(d

.)

619

3 C

fiH,

N=N

C6H

s C

H3

CO

OH

I

a

M. 20

6-20

7"

(d.)

27

2

'6'5

CO

OC

,H,

Ia

M

. 14

8-14

9"

227

C6

H5

C

OO

H

XIV

a

M.

179"

17

1

N.

R

R

~

R"

~~~~

~~~

-~

~

.-

-~ ~~

~~

-~

Met

hod

s of

X

sy

nth

esis

M

.p.

or

B.p

. R

efer

ence

s D

eriv

ati

ves

1H

C

H3

CO

OC

2H5

XIX

d

M. 17

2"

165

C6

H5

N

=NC

,H,

CH

3 C

N

VII

a

M. 13

0"

419

3 D

o.

-

N=N

C6H

5 C

H 3

CO

OH

X

VII

a

M. 2

05"

419

4 C

6H5

N=N

C6H

5 C

6H

5

CN

V

II a

M

. 204

-205

" 41

9

4 0

;

x

e:

842

z N

3

3 0

s N 0 N

L (D 3

W N 3

3

3 CQ

2 2 s 2

rd rd

0 V

k- * E E

x * v) N N

rd

E d

E

m 3 N * 3 3 0 L- 03 m 3

e 3

843

d a l. 0 9

X

L- LD N

P L- 3

cb r 4

2

P

844

0 0 0 l n r n r n N N N

n n

d i ! 8 V

8

5 : 5 : % N N N

m

O N N 3

o ; b

Z ' E '

f 8 8

3 3

* * m r n N N

m m 3

s

8

m 3 N 3

845

c 5 3

U .3 3

a:

L- W L-

3 N n *

Xi u

Lc

846

m 3

N

2

2 z c

c c .3

c

4 m

e:

e:

I I

cr;

cr;

Q ' z

I

m N

848

m W L- W W 3 t- i

t-

W (D t- t- W t- t- W L-

m t- 3 R

W 3 N v) 3

3 Ln I I m

W 3

I t- L-

Q

iZ , I I 2-0

o" Y

n

x V

cn N

5: m

t- N W N

51

co N 4 m 0 m

849

w

850

TA

BL

E 1

04.

Su

bst

itu

ted

Nit

roso

py

razo

les

a)

4-n

itro

so

:xJfR

' I

N.

R

R'

1

2 3 4 5 6 7 8 9 10

11

CH

3 c1

H

CH

3

C6

H5

H

R"

Met

ho

ds

of

syn

thes

is

Ref

eren

ces

M.p

. o

r B

.p.

Dy

-iv

ativ

es

CH

3

OC

2H5

SCH

,

SCH

,

SCH

,

'IjH

5

SeC

H,

SeC

H,

,CH

, -N

,

-$ C

6H

5

CH

3

'6'5 ,CH

3 -

XIX

c

XV

UI e

XIX

c

XM c

xrx

c

XM

C

XIX

c

XM c

XIX

c

XM

C

XIX

C

M. 8

7"

883

M.

( 126

-127

" (d

.)

1058

1-10

0"

(d.)

696

M.

137"

68

3

M. 9

6"

683

720

M. 14

8" (

d.)

686

M.

117.

5"

M.

136"

68

9

M. 9

9"

67 3

M.

135"

69

6

M. 8

9"

699

.HC

1: M. 1

56"

TABLE 1

04 (

con

td.)

~_

__

__

__

~_

__

__

_ - __

_

_ _

__

~

Met

hod

s of

N.

R

R'

R"

S

ynth

esis

M

.p. o

r B

.p .

Ref

eren

ces

Der

ati

ves

12

C,H

, C

H3

F2

H5

-N

''6HS

XM

c

M. 9

8"

699

.HC

1: M

. 14

0" (

d.)

XIX

c

M. 1

51

" 7

18

XM

c

M. 7

3'

699

.HC

1: M

. 1

29

CH,C

,H,

15

C,H

, C

H3

-N:

X

IX

C

M. 7

0"

699

.HC

l:M

1

34

-

'IiH

5

N.

R'

R"

R

16

C,H

, -N

=C(C

H,)C

H=C

(CH

, 1-

17

C,H,

-N(C

H,)C

H=C

HC

&

18

C,H

, -N

(CH

, )C

H=C

(CH

, )c

(r

19

C,H

, -N

(CH

, )C(COOH)=CHCC~

20

C

,H,

-N(C

H, )C(COOH)=C(CH, )C

O-

XM

c

M. 2

30"

(d.)

2

61

XM

c

M.

253"

26

2

XIX

c

M. 2

59"

262

xu( c

M

. 17

4

262

XIX

c

M. 2

55"

262

b)

N-n

itro

so

11“’ “-BI;”

N’ k0

N.

R

R’

R”

Met

ho

ds

01

syn

thes

is

M.p

. or

B.p

. R

efer

ence

s D

eriv

ativ

es

1

cI13

2 C

H,

XM

c

M.

40”

XM c

M

. 34”

1058

1058

W

cn

w

TA

BL

E 1

05.

Su

bst

itu

ted

Acy

lpyr

azol

es

N.

R

R'

R

~ ~~

Met

hod

s of

X

syn

thes

is

M.p

. or

B.p

. R

efer

ence

s D

eriv

ati

ves

1

2 3 4 5 6 7 8 9 10

11

12

c1

H

H o

r C

H,

H

CH

,

H

CH

,

CH

,

C6H

5

Br

OC

OC

H,

CfiH

5

H

c1

c1

Br

Br

I I 3

H

Br

H

H

C6H

5

H

CH

, o

r H

H

CH

,

H

CH

,

c1

c1

Br

Cfi

H5

OC

OC

H,

CO

CH

,

CO

CH

,

CO

CH

,

CO

CH

,

CO

CH

,

CO

CH

,

CO

CH

,

CO

CH

a

CO

CH

,

CO

CH

,

CO

CH

,

CO

CH

,

M. 7

5-7

6"

XX

Ve

M

. 72

-74

"

XX

V e

M

. 34

"

XX

V e

B. 7

7. 5

"/9

XX

V e

M

. 93-

94"

M.

38"

XX

V e

M

. 114

"

XX

V e

XX

V e

M

. 20-

21"

M. 6

2. 5

-63.

5"

B. 2

01-2

02"

XX

V e

M

. 69

-70"

XX

V e

M

. 106

"

XV

III

b

M. 7

5-7

6"

XX

V e

-XX

VI

a

XX

V e

M

. 84

"

79

501,

504

51

50

1

7 39

56

1

739

79

,70

8

79

501

10

28

10

28

10

28

13

C,H

,

14

C,H

,

15

C

,H,

16

C

,H,

17

H

18

C

H,

19

20

21

22

23

24

25

26

m

cn

27

v1

28

CH

3

C,H

, o

r C

1

CH

, o

r H

CH

3

CH

3

OC

OC

,H,

H

CH

,

C6

H5

H

H

H

H

H c1

H

CH

3

H c1

Br

I H

OC

OC

,H,

H

H

NH

CO

C,H

,

CO

CH

,

C?o

c,H

, -N

=CH

-CH

C

OC

H,

"C,H

5

HS

CO

&

OC

H,

H

cocc

1,

c1

CO

C,H

,

c1

C1

or

C,H

,

H o

r C

H,

CH

,

CH

,

C6

H5

H

OC

OC

tiH5

OC

OC

,H,

H

XX

VI

a 10

28

XX

V e

M

. 10

8-10

9"

1028

XX

V e

M

. 16

9"

263

XX

V e

M

. 12

3-12

4"

262

XX

V e

-XX

VI

b M

. 24

2-24

4"

263

XX

V e

XX

V e

XX

V e

XX

V e

XX

V e

XX

V e

XX

V e

XX

V e

XX

V e

-XX

VI

a

M.

53-5

4"

M. 2

6"

B.

302"

B. 2

18-2

20"/

60

M.

90-9

1"

M.

89-9

0"

M. 4

8-49

"

M.

48-4

9"

M. 82

"

M.

181-

182"

M. 1

09"

XX

V e

-XX

VI

a M. 1

28-1

29"

XX

V e

M

. 11

7-11

8"

XX

V e

-XX

VI b M. 17

3"

504

79,7

08

883

79

51

739

739

1028

1060

778,

naz

1028

1062

cv m m

t- W 3

2

d

E x

m t-

m m

I m m

3

3

2

Y

> X x

In

xu 6 v v

m 0 m N

3 LD

b m

I m

3

t- 3

2

m

0

I

X 4

V

G

V

X

k

N m

m t-

b

I m m

v 3

3

2

m > 8

% a , 0 0

I

G

$I

Em V

m m

m m r- t-

LD

m' N 3 3

I I In N M 3

3 i

m 3

N N ( D W N N

m to N

b v

R m

m I " 0 7

A X h i 2 2

N

W N

B " I

X X 5: x x

4

a 1

xm ?.a V V V

t - w m m m W m m - m

39

C,H,

H

-N(CH~)C(CH,)=CHCO-

XX

VI

b

M. 2

42-2

43"

260

40

C,H,

H

-N(CH,)C(COOH)=CHCO-

XX

VI

b

M.

172-

175"

(d

.)

262

41

C,H,

H -N(CH,)CH=C(CH,)CO-

VII

I M

. 19

2-19

4"

262

XX

VI

b

42

C,H,

H

-N(CH,)C(COOH)=C(CH,)C&

XX

VI

h M

. 27

2-27

4"

262

N.

R

R'

R"

X

Met

ho

ds

of

syn

thes

is

M.p

. o

r B

.p.

Ref

eren

ces

Der

ivat

ives

C6HS

CH

3 c1

CHO

XV

U b

M

. 14

2-14

3"

885

Ph

eny

lhy

dra

zon

e:

M.

174"

88

5

Sem

icar

baz

on

e :

XX

III g

M.

214-

215"

CHO

XX

III g

M.

103-

104"

88

5 S

emic

arb

azo

ne :

M.

182"

Gu

any

lhy

dra

- zo

ne.

HN

03

:

M.

204-

205"

C6H5

c1

CH

3

C6

HS

N=NC6Hs

CH3

m

Ln 4

'CiH5

N=NC,H,

CH20C6Hs

COCH,

VII

a M

. 17

9"

COCH,

VII

a

M.

178"

419

p -n

itro

ph

eny

l-

hy

dra

zon

e:

M. 2

22"

Sem

icar

baz

on

e :

M.

193-

194"

419

p-N

itro

ph

eny

l-

hy

dra

zon

e :

M. 21

8-21

9"

m i co

m

i N 3

I 0 N 3

2

d b-

5

f u

$ u

d A I// 9 I

5 m

16

17

18

19

20

21

22

23

24

25

m

26

cn

(D

H5C

6C0

-s

s

b5

SeC

H,

SeC

,H5

SeC

H,C

OO

H

SeC

H,C

,H5

SeC

OC

GH

s

v c2

XX

I f

XX

VI

a

XX

VI

a

XX

VI

a

XX

VI

a

XX

VI

a

XX

I f

XX

b

XX

b

XX

b

*

M. 156”

M. 7

0“

M. 84“

M. 157”

M. 146”

M. 11

1“

M. 141”

M. 125”

M. 201”

M. 78

”

M. 126”

666

666

697

697

697

697

697

697

697

697

697

697

* F

rom

l-p

heny

l-3-methyl-4-benzoylpyrazole-5-selen

ic ac

id b

y tr

eatm

ent

wit

h SO

,, o

r fr

om

bis-[l-phenyl-3-methyl-4-benzoylpyrazolyl-(5)]-

dise

lani

dete

trab

rom

ide by t

reat

men

t w

ith N

aOH

.

TABLE 105 (

cont

d.)

N.

R

R'

R"

Met

ho

ds

of

X

syn

thes

is

M.p

. or

B.

p.

Ref

eren

ces

Der

ivat

ives

27

28

29

30

31

32

33

34

35

C6

H5

C6

H5

'fiH

5

C6

H5

C6

H5

Se0

3H

C

OC

6H

5

OC

OC

6H5

CO

C6

H5

CH

3 c1

C

OC

6H

5

C6

H5

c1

C

OC

6H

5

c1

CO

C6

H5

N(C

H&

H,C

H,)

, C

OC

6H

5

CO

C6

H5

HO

\

c1

XX

I h

XX

V e

XX

VI

a

V b2

XXV e

XX

V e

XX

Ve

v c4

Ix

XM d

XX

Ve

M. 152"

M 157"

M. 88"

B. 245"/15

M. 127"

B. 340-345"/25

M. 70"

M. 144. 5"

M. 164"

M. 110"

697

679,688,785

981

679, 688, 785,

981

679,697

Ph

eny

lhy

dra

zon

e:

442,708

882

M. 176"

882

679

688

708

708

m 0 t-

b t-

i

k

8

m 0 t-

m 0 t-

. b

m m

k 9

+q 0 = o

Y I

m 0 t-

0 0 * 2-

$ 0

$ a

il

f$ 0

8 G G G G G

86 1

cd d r n d w w w m w o ( D m m 3 n N

r3 t- 3

9

- F - F d a m - 3 * * * 3

0

XW V

X 0

m

Ew X

N n

g g m m N N 2 %

rd

F cd

a x I X : g

5: !-

X m

D.7 8

8 8 8

(D Ln

r d d

W W W W m m

b w * i

50 5-

0 d 0 J

3 N

m m m m W W

m W W

W 3 *

rd

m W co

N r- 3

2

Q

m W N

i

8 %- " 5

Ln

wz- I 1 /

W

863

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3=N

H 3

OSH

N-

OS=

N

'H'303H

N

F9

Z

VH

~)

H~

~H

H~

~~

HN

c~

~3

~~

'H93H

NS

3HN

'Hg3H

N03H

N

'HN

O~

HN

OH

3HN

HO

N=

N

ZH

N

'H

~O

~H

N

"H

N

'H'3H

3-N

EH

3

JH

I3

13

13

13

'H3

9

HS

'H93 P

'H93 E

'H3

'H93

Z

EH

3 H

I

X

..n

.H

n .N

N(C

H$

~

XX

VI

a

M. 55-56"

B.1

22-1

26"

/1, 5

M. 64-65'

B. 154-156"/2

M. 1Y

596

596

OC

HZ

CsH

5 xx

vl a

xxV

I a

596

10

CH

, xx

vl a

M. 10

0"

596

NH

CO

C6H

5

NH

CO

C6H

,

NH

SO,C

,H,

XX

VI

a-b

XX

VI a-b

XX

vl

a-b

M. 176-

M. 18

8'

M. 17

1"

69 5

116

895

13

C6H

5

14

C6H

5 N

(CO

CH

,),

XX

VI

a-b

-Vm

M. 134.5-135. 5'

484

XX

VI

a-b

M. 193'

695

XX

vl a-b

XX

llI

c

XX

Vl

b

XX

VI

b

XX

vl b

XX

VI

a-b

XX

W a

-b

M. 159"

Oil

M. 99"

M. 163-164'

M. 11

5-

M. 109-110-

M. 153-154"

M. 122-123"

69 5

1096

1096

1096

1098

1096

1096

1098

.HC

I :

M. 183-184-

OC

OO

CH

,

OC

OC

H,C

H(C

H3)

2

FJr I

-C€O

CH

CH

(CH

,),

OC

OC

,H,

21

C,H

,

22

C6H

5

23

C6H

5

%

24

C,H

,

-NH

CO

CH

CH

(CH

,),

NH

CO

C,H

,

XX

vl a

-b

XX

VI

a-b

XX

IU b

-XX

VIb

XX

VI b

M. 114-116"

M. 196'

M 230"

M 167-168"

1098

46

1096

1096

4C

H2

CO

NH

-

--O

CH

~C

ON

(CH

,~

* F

rom

l-p

heny

l-3-

methyl

-4-a

mino

-B-e

thox

y-py

raza

le

by

trea

tmen

t w

ith

form

alde

hyde

and

HC

N

c

9

I

m

Q -

!

! I

L d $ 2 2 r" r" u u u

P

d j

t- 2 4

r r * * 3 3 4 3

s

5 5

m m m m

G G G G x M M M M

868

m m 3 2 N

3 3 m v ) ( 0 -

3 In (0

N v) v) 3 3 3 3 3 - 3 + r w co m v ) l n l n v ) r n r n l n w (D w w w w w iD w w w

d 3 3 v) m u ? w w ( D

0" 2"

@ a m 3 3

0 3 m 3 d

869

N N

W W w w w w w v) I ( 3 3 “ N L n m m v ) m i m i m w

4 2

1 1

a i o

c) S

ub

stit

ute

d T

hio

py

razo

les

not

com

pri

sed

in

th

e p

rece

din

g t

able

s

N.

Co

mp

ou

nd

s M

eth

od

s of

sy

nth

esis

M

.p. o

r B

.p.

Ref

eren

ces

Der

ivat

ives

-

XIX

a

M. 1

07"

655

1

IV c

M

17

9"

649

XX

VI

a

M.

190"

69

2

* CD * m Ln (D

m v) (0

l l

N m

m 4

P

TA

BL

E 1

09 (

con

td.)

N.

R

R'

R"

BI

Br

N=N

C,H

,

N=

NC

6H5

N=

NC

,H5

X

OC

OC

,Hs

OH

OC

H,

OC

2H5

OC

OC

6H5

OC

H,

OC

2HS

OC

H,

Met

hod

s of

sy

nth

esis

XTX

a

XX

VI

a

* XX

VI

a

XX

VI

a

XX

VI

a

XX

VI

a

**

XX

VI

a

XX

VI

a

XX

VI

a

Mp

.or

B.p

R

rfer

ence

s D

eriv

ati

ves

M. 7

8"

M.

142"

M.

80"

M.

137'

M.

119"

M. 82

. 5

785

785

509

La

cto

ne

47

281

281

46

47

281

M. 98'

M.

204"

281

281

9 C

6H5

(CH

OH

),C

H,O

H

N=N

CsH

5 O

CH

, X

XV

I a

M

165-

166"

79

9

N=N

CsH

5 oc

n,

XX

VI

a M

. 12

1-12

3"

484

10

C6H

S 73-

484

M. 15

4-15

5"

l1

'6jH

S

N=N

C,H

, O

CO

CH

, X

XV

Ia

N=N

C,H

, O

CH

, XXVI e

M. 12

2- 1

23"

484

XXVI a

-VII

l

c) S

ubst

itut

ed H

yd

rox

yp

yra

zole

s no

t C

om

pri

sed

in t

he

Pre

ced

ing

Tab

les

N.

Com

poun

ds

Met

hods

of

syn

thes

is

XM

d

M.p

. o

r B

.p.

Ref

eren

ces

Der

ivat

ives

M.

122-

125"

M. 9

3"

1059

219

* F

rom

1,4-dibromo-3-methylpyrazol

-5-o

ile w

ith

NaO

H.

* * F

rom

1 phe

nyl-

3-me

thyl

-4,5

-dio

xopyrazoline wit

h (I -k

nzo

ylp

hen

ylh

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SUBJECT INDEX

The letter trrrt after a page number indicates ?reaction(s)", and the letter "s" indicates "synthesis".

Acetylenic carbonyls, in pyrazole

Acelytenic derivatives, synthesis 16-19

addition to pyrazoles 78-80 in pyrazole synthesis 26-28,

in pyrazoline synthesis 205-6 41, 59-62

Aldehyde arylhydrazoles, in pyrazole synthesis 23-6

Alkylation of pyrazoles 71-3 Arndt-Eistert synthesis 139 Azomethine imine addition,

in pyrazolidine synthesis 280 in pyrazoline synthesis 205-6

Aziridines, in pyrazoline synthesis 186-7

Buchner-Curtius cyclopropane synthesis 209

Cannizzaro reaction 125 Carbonyls,

a-halo, in pyrazole synthesis

a, p-unsaturated, in pyrazoline synthesis 181-5,

20-23

189-90 Chromic acid oxidation,

of pyrazoles 66-7,70 of pyrazole thioesters 135

Claisen condensation 120 Cyclopropanes, f rom pyrazolines

209-13

Diazoalkanes, in pyrazoline syn-

Diazo compounds, thesis 195-205

Aliphatic, in pyrazole synthesis

26-34,82-3

Diazo compounds-cont. Aliphatic-cont .

in pyrazoline synthesis 195-206

aromatic, in pyrazole synthesis

Diazonium salts, aryl- , in pyrazo-

p-Dicarbonyl, in pyrazole synthe-

Diels-Alder reaction 178, 279 Dipyrazole sulfides 134s

34-5

line synthesis 207

sis 10-16, 33,82

Enamines, in pyrazole synthesis

Epoxides, in pyrazole synthesis

Ethylene imines, in pyrazole syn-

40-41

57-8

thesis 58, 59

Fridel-Crafts reaction 110, 119, 121, 342

ct-Halocarbonyls, in pyrazole syn-

Halovinyl derivatives, in pyrazole

Hydrazides, thiocarbo-, i n pyrazole

Hydrazine and derivatives,

thesis 20-23

synthesis 28-31

synthesis 20-23

in pyrazole synthesis 10-20,

in pyrazolidine synthesis

in pyrazoline synthesis

53-59

282-3

180-195

88 1



Subject Index

Hydrazones, in indazole synthesis

Hydrazonic halides, in pyrazole synthesis 35-41

304-5

Indazole, 1-acetyl- 293 acetylation 3 15-6 1-acetyl-3-methyl- 303s acylation 340 3-amino- 299s) 335s, 344s,

3451%) 3481- 5-, 6-, 7-amino- 309r association 293 3-benzyl- 304s bromination 305 3-bromo- 325rs 5-bromo- 325s 7 -bromo-6 -hydroxy- 308r chlorination 324 3-chloro- 324s-5r) 348s 4-chloro- 325rs 5-chloro- 325s chioru-3 -hjidrmy - 301 s 3-cyano- 299s

5,6-dihydroxy- 308r 5,7-dimethyl- 295s 5, 7-dinitro- 300s 3-duryl- 304s 4-fluoro- 300s 3-halo- 305s halogenation 324 2 -hydroxy - 33 5r s 4-hydroxy- 338rs 5-hydroxy- 338rs 6-hydroxy- 308r, 339rs 7-hydroxy- 300s) 339rs 3 -hydroxy - 2 -phenyi - 3-iodo- 325rs, 348s 3-mesityl- 304s 1 -methyl -,

4-Cyano- 343s

302 s, 336s

association 293 reduction 318

bromination 308 reduction 318

2-methyl-,

Indazole-cod. 5-methyl-,

bromination 308 nitration 308

nitration 308, 329 4-nitro- 308r, 328rs-9r 5-nitro- 308s, 329rs

halogenation 308 nomenclature 293-4

6-nitro- 308r, 329rs 5-nitro-1-benzoyl- 304s nitro -3 -bromo-, isomerism

6-nitro-1, 3-diphenyl- 304s 5 -nitro-3 -methyl- 304s 4 -nitro- 1 -phenyl- 320s 4 -nitro-2-phenyl- 303s nitrosation 309 1-phenyl- 320rs-21r 2-phenyl- 321s, 322r

nitration 308 sulfonation 309

292

3-phenyl- 304s, 322-3s, 323-41-

isomerism 291, 323 physical properties 317 reactions 318-9,341,355 reduction 3 18 side-chain acids 343 sulfonation 309 synthesis 295, 299, 300, 317-8 t e t r ahydro - 36 2r s

1H-Indazole 289, 293 2H-Indazole 289,293 3H-Indazole 290, 355-6 Indazole- 3-acetic acid,

bromination 308 reactions 343-4 synthesis 343

Indazolecarboxamides, synthesis

Indazolecarboxylic acids 340-44 Indazole-3 -carboxylic acids,

reactions 325,341-2 synthesis 300,341, 342-3

Indazole -1 -oxides, reactions 354-5 synthesis 304, 353-4

Indazoles 289-365 1-acetyl- 303s

341

882

Subject Index

Indazoles-cont. acylation 315-17 alkyl- 320 alkylation 309-15 amino- 344-51

sulfonation 309 3-amino- 295s) 299s) 344s)

3451- aryl- 303s 1-aryl- 320s 2-aryl- 299s) 301-2s) 321-2s)

3221- 3-aryl- 322-3s arylation 314 2 -aryl- 3 -hydroxy - 302s)

336s) 3371- 3 -aryl-2-hydroxy- 336rs 1-benzyl- 320r halo- 324-8 3-halo- 308s halogenation 305, 308 hydroxy- 309r, 335-40 nitration 308-9 nitro- 328-35,348r nomenclature 293-4 of biochemical interest 352-3 reduced 362-5 ring substitutions 305-17 structure 289-93 sulfonation 309 synthesis 294-305

by N-1, C-3 closure

by N-1, C-7a closure

by N-1, N-2 closure 303-4 classification 294

295-302

304 - 5

tetrahydro- 362s) 363-41- Indazole -4-sulfonic acid, synthesis

Indazole -7 -sulfonic acid, synthe-

Indazolesulfonic acids 351-2 6-substituted 339s

Indazoletriazolene 348 Indazolium halides 314-5 Indazolone,

351

sis, 309

physical properties 352 reactions 358 synthesis 289, 357

Indazolones 356 -61 reactions 358 synthesis 357-8 tautomerism 356 tetrahydro- 363

Indiazene 355 Indiazole 290, 355 Isoindazole 290, 293 Isopyrazole, 3, 4, 4, 5-tetramethyl-,

Isopyrazoles, bromination 86

pyrazoles from 49-52 stability 4 synthesis 28

Isothiopyrones, pyrazole s f r o m

Isoxazoles, pyrazoles f rom 56 64

p-Keto esters , in pyrazole synthe-

Ketomethylene compounds, in

Ketones,

sis 23-6, 33

pyrazole synthesis 33-4

a -epoxy -, in pyrazoline synthe - sis 190

0-substituted, in pyrazoline synthesis 185-6, 190-91

Kishner cyclopropane synthesis 209

Knorr pyrazoline test 179 Kolbe synthesis 339

Malonic derivatives, in pyrazole

Mannich bases 185 Mannich reaction 80 Methyl pyrazole-3,4, 5 - t r i ca r -

synthesis 32-3

boxylate 115

Nitration of pyrazoles 95,96 Nitric oxide oxidation of pyrazoles

Nitriles, a, p-unsaturated, i n py ra -

Nitrosation of pyrazoles 91 Nitrovinyl derivatives, in pyrazole

synthesis 28-31

66

zoline synthesis 185, 191

883

Subject Index

Oxidation, of pyrazoles 65-67 of pyrazolines 215-21

Oxidative cleavage of pyrazole

Oxiranes, in pyrazoline synthesis

Ozone oxidation of pyrazoles

ring 70

186-7

67,71

Pe rmanganate oxidation, of pyrazoles 65-6,70,75 of pyrazole thioesters 135 of pyrazolines 106, 216

N-acyl-, isomerism 138-9 5-alkoxy- 16s 3-alkylmercapto- 20s 5-azo- 101s 3 -benzoyl-4-phenyl- 34s 3-benzyl-5-phenyl-4-diazo-

4 -bromo-3 -methyl- 85s 3 -carboxy -5-methyl - 72r 4-chloro-3-methyl- 85s diazo- 105s 3,4-dibenzoyl- 124s 4, 5-dibromo-3-methyl- 85s 1,3-dimethyl- 216s 1, 5-dimethyl- 86r 3, 4-dimethyl- 86r 3, 5-dimethyl- 105r 3, 5-dimethyl-4-amino- 1041- 3, 5 -dimethyl -4 -diazo- 105s 3, 4-dimethyl-5-iodo- 86s 3, 5-dimethyl-4-nitro- 56-7s 1, 3-diphenyl- 45s 3, 5-diphenyl 70r 3(5)-halo- 73r 4-halo- 84-5s halogenation 84-5 hydrogenation 02 hydroxy- 87r 4 -hydroxy - 32s 4-hydroxy-3, 5-dimethyl- 20s 3-iodo-4 -methyl- 85s 4-mercapto- 23s methyl- 30s 1-methyl- 84r

Pyrazole 81-2

105-6r

884

Pyrazole-cod. 3-methyl- 20S, 26s, 85r 4-methyl- 85r 3 -methyl-4-o -arninophenyl-

54s 3-methyl-1, 5-diphenyl- 11s 1-methyl-5-phenyl- 18s 3( 5) -methyl-4 -phenyl - 2 17s 3-nitro- 35s 1 -p -nitropheny1-5-phenyl- 13s 3 -nitro- 5-P-pyridyl- 701- oxidation 82 1-phenyl- 62s) 135r

bromination 87 reduction 68,70-71

1 -phenyl-3, 5-dimethyl- 68r 1-phenyl-3-methyl- 12s) 701- 1 -phenyl-5-methyl- 12s phenylthienyl- 96r physical properties 81,82 pyrazolo[ 3,4-d] - 106s reduction 70 sal t formation 81-2 synthesis 30, 57,81,216 tautomers 4 tetrahydro- -see Pyrazolidine 1, 3, 4, 5-tetramethyl- 77s)

thioesters 135r 1-p-tolyl- 45s) 68r, 70-71r 1, 3,4-trtiodo- 85s trimethyl- 1061- 1, 3, 5-trimethyl- 77s 3, 4, 5-trimethyl- 53s) 1121- trimethylamino- 106s 3, 4, 5-trimethyl-1-phenyl-

Pyrazole -4-aldehydes, synthesis

Pyrazole -5-aldehydes, synthesis

Pyrazole azo dyes, from pyrazo-

Pyrazole -4 -carbony1 chlorides,

86r

217s

122

123

lines 216

Friedel-Crafts reaction 121

106-17 Pyrazolecarboxylic acids

effect of heat 115 from 2-pyrazolines 216

Subject Index

Pyrazolecarboxylic acids-cont. physical properties 114-5 reactions 114-7

Pyrozole- 1-carboxylic acids, synthesis 113-4

Pyrazole -3 -carboxylic acids, effect of heat 115-6 synthesis 56, 84, 106-7

Pyrazole -4 -carboxylic acids, effect of heat 115 synthesis 84, 107-8

Pyrazole -5-carboxylic acids, syn-

Pyrazole-3-carboxylic es ters ,

Pyrazole-4-carboxylic es ters ,

3,4-Pyrazoledialdehyde, synthesis

Pyrazolediazonium sa l t s 104-6 Pyrazole -3,4-dicarboxylic acids,

thesis 109

Claisen condensation 120

synthesis 23

124

1 -phenyl- 1161- synthesis 109-10

4-methyl- 112s 1-phenyl- 115r, 1161- synthesis 11 1-12

Pyrazole -3, 5-dicarboxylic acids,

Pyrazole-4, 5-dicarboxylic acids, synthesis 110-11

Pyrazole disulfones, synthesis 135

Pyrazolenine, stability 4 Pyrazoles 3 - 139

3-acetyl- 119s acyl- 125-61- 1-acyl- 12s 3-acyl- 117-21s 4-acyl- 121-3s 5-acyl- 123-4s N-acyl- 137-39s, 139-40r 3-acyl-1-aryl- 120s 4 -acyl - 5-acyloxy- 1 2 2 s acyloxy - 128 - 30s acylseleno- 132s acylthio 132 alkoxy 1.31-21- 5-alkoxy- 130s alkyl- 82-3s

metalation 83-4 salt formation 83 stability 83

Pyrazoles- cont. 1 -alkyl- 109r 4-alkyl- 40s) 41s alkylamino- 104s alkylation 71-3, 78-80 alkylmercapto- 133s, 133-4r a1 kylthio- 132 -4s amino- 56s, 102-6 3-amino- 98r, 103 4-amino- 103s 5-amino- 36s) 56s, 103. aminoalkyl- 104 aminoarylamino- 103s aryl- 82-3s

metalation 83-4 salt formation 83 stability 83

1-aryl- 57s arylazo- 98s 4-arylazo- 20s) 104 N-arylsulf onyl- 140 azo- 101-2r, 103r 3-azo- 98-9s 4-azo- 99-100s N-benzyl- 76-71- 4-bromo- 89s) 90r, 91r, 107r 5-bromo- 89s carbonyl derivatives 117-26 4 -carboxy - 5-carboxy- 109s chemistry 81-140 5-chloro-4-hydroxy- 128s 4-chloromethyl- 1231-

de a1 ky lation 7 3 - 8 3, 5-diacetyl- 124s diaryl-, spectra 9 dihydro- -see Pyrazolines dimethyl- 10-11s) l l l r 3,4-dinitro- 97r 1,4-dinitro-3-methyl- 95s 1, 3-diphenyl- 45s 1, 5-diphenyl-3-methyl- 68r 1 , 3 -diphenyl-5 -methyl- 68r general reactions 65-80 halo- 84-91 4-halo- 1071- hydrazo- 102s hydroxy- 126-32 1-hydroxymethyl- 741- imino- 102

1 lor, 11 5 r

4-CyaO- 90s

885

Subject Index

Pyrazole s-cont . isomerism 6 -9 naturally occurring 3 nitration 95-6 nitro- 93-7s) 97r, 103r 3-nitro- 93-4s 4-nitro- 66s) 90s N-nitro- 95s nitroso- 91-2s

chemical properties 92-3 oxidation 66, 92, 97 physical properties 92 reduction 93,97,103

oxidation 65-7 phenyl- 57s) 95-61- polyacyl- 124-5 reduction,

to pyrazolidines 281 t o pyrazolines 206-7

ring cleavage 70-71 ring reduction 67-70 selenium derivatives 137 sulfonation 13 5 sulfur derivatives 132-7 synthesis,

by 4,5 ring closure 19-20 from acetylenic carbonyls

with hydrazines 16-19 from aldehyde arylhydra-

zones with p-keto e s t e r s

f rom diazo compounds

from /3-dicarbonyls with hydrazines 10-16

from epoxides and ethylene imines 57-9

from a-halocarbonyls with thiocarbohydrazides

f rom heterocyclic com -

f rom hydrazonic halides

f rom isopyrazoles 49-52 from pyrazolines 41-9,

f rom pyrazolones 62-3 from syndones 59-62 from 1, 2, 3, -tricarbonyls

with hydrazines 20

23-6

26-35

20-23

pounds 53-7

35-41

52-3, 215-17, 219

886

Pyrazoles- cont. tautomerism 4-6 trichloromethyl- 106r 1,3,5-triphenyl- 68r N-unsubstituted 78-91-

Pyrazolesulfinic acids 136 Pyrazolesulfonamide, synthesis

Pyrazole-3(5)-sulfonic acid 216 Pyrazolesulf onic acids,

reactions 136 synthesis 135-6

216

Pyrazole sulfones, synthesis 135 Pyrazole sulf oxide s, synthesis

135 Pyrazolethiones,

oxidation 135 pyrazoles from 62-5,133

Pyrazole-3,4,5-tricarboxylic

Pyrazolidine, acids, synthesis 112-13

3,5-dimethyl- 281s 1,2-diphenyl- 282s) 283s perfluoro- 283s 1 -phenyl- 283s 1 -phenyi-4 -allyl- 283s 1 -phenyl-4-hydroxy- 283s 1 -phenyl-3 -methyl- 281s 3 -phenyl- 5-styryl- 281s physical properties 279 synthesis 282

Pyrazolidines 279-84 chemistry 284 oxidation 207 synthesis,

by ring fusion 279-80 by reduction 69,70, 281 by cyclizations 281, 282-3

Py r azolidone s) pyrazoles from 63 synthesis 216, 223

1,2 -dimethyl-5 -phenyl 2811- history 179 5-hydroxy- 52s oxidation 2 15 3(5) -phenyl- 194 -5s reactions 221-3 stability in air 209, 221 synthesis 178

Pyrazoline,

Subject Index

1 -Pyrazoline, 3,4-dibenzoyl- 298s perfluoro- 283

1-aryl- 181s 3,3' -bis- 1 -phenyl-, spectrum

2 24 4 -n-butoxy - 205s 5-carbethoxy-3-phenyl- 215r 3 -carbomet hoxy - 3,4-dibenzoyl- 198s 3,4 -dicarbomethoxy 196 1,5-dimethyl- 191s, 216r 1,3-dimethyl-4-bromo- 191s 1,5-diphenyl- 180s ~

1,5-diphenyl-3 -methyl- 206s 4-hydroxy- 186s 5-methyl- 2141- 1-phenyl- 181s, 182s, 222-31-

2-Pyrazoline,

2 12 - 13r

nitrosation 221 oxidation 215, 220

3-phenyl- 183r, 205s rearrangement 222

5-phenyl- 189s isomerization 214 rearrangement 2 2 2

1 -phenyl- 3 -methyl- 182s, 206s, 2201-

1 -phenyl-5-methyl- 182s, 215r

synthesis 70, 204 1-o-tolyl- 2211- 3,5,5-triethyl- 2161- 3,5,5-trimethyl- 2221- 1,3,5-triphenyl- 185s, 2151.

Pyrazolinecarboxylic acids, oxida-

Pyrazoline diazoketones, synthesis

Pyrazoline -3, 5-dicarboxylates,

Pyrazoline-N-oxides 207, 220 Py razoline s

tion 106

204

.. oxidation 11 1

177 - 26 7 acyl- 1201- alkyl- 1061- chemistry 209-25 history 179 4 -hydroxy 57s isomerism 178 oxidation 215-21

to pyrazoles 41-9

Pyrazolines-cont. pyrolysis 209-14 2-pyrones from 213 reduction to pyrazolidines

28 1 reductive cleavage 221 spectra 223-5 synthesis,

cyclization based 192 from aliphatic diazo corn - from aliphatic hydrazines

from arylhydrazines

from pyrazoles 68-71,

from pyrazolidines 207 miscellaneous 206-8

po)i"ds 195-206

189-92

181-9

206-7

taut ome ri sm uses 225

cyclopropanes from 209 fused-ring 207s ' isomerization 198-200, 202 N elimination 210 oxidation 220 spectra 223 synthesis 178, 204 tautomerism 197-8, 211

acetylation 221 alkylation 221-2 l-alkyl-2-phenyl-, spec t r a

224 3-amino- 223s 1H-3-amino- 191s 1-aryl- 2201- 1 -aryl-3-amino- 185s 1 -aryl-3-arylazo- 207s benzoylation 221 bicyclic 190s bis- 220 1 -carbamyl- 190s

spectra 223 3-carboalkoxy-, spectra 224 cyclopropanes f rom 209 1 -( 2,4 -dinitropheny 1) -

5, 5-diphenyl- 205s 1H-4-hgdroxy- 191s

1 7 7 - 8, 2 14 - 1 5

1 -Pyrazolines,

2 -Pyrazolines,

183-4s

887

Subject Index

2-Pyrazolines- cont. 3-methyl- 223 nitrosation 221 1-nitroso- 221r oxidation 216 4-phenylazo- 222-3 1-phenyl-4-hydroxy- 186s 1 -phenyl- 5-hydroxy- 2171- 1 -phenyl-5-substituted 2231- pyrazoles from 216 reactions,

a t position 1 221-2 a t position 3 222-3

spectra 223-4 synthesis 68, 178 tautomerism 211 1, 3, 5-triaryl-,

flourescence 224-5 spectra 224

3-Pyrazolines 178-9 spectra 224 synthesis 194-9, 205

oxidation 216 2 -Pyrazoline -3 -sulfonate, n -butyl-,

Pyrazolium salts, alky lm e r capto - amino- 104r 5-chloro- 104 dealkylation 75-6,77-8 3(5)-halo- 136r reduction 69 reductive cleavage 71 synthesis from pyrazolones

1 3 3 - 4 r

72 5 -PyrazoIone,

3-phenyl- 129r, 130r 1 -phenyl- 3 -methyl-

alkylation 130 imino-, tautomerism 104-5 oxidative cleavage 220-21

28 1 r Pyrazolones,

Pyrazolones- cont. pyrazoles from 62-4,87-8 reduction to pyrazolidines

synthesis 16, 36 thio- 132r

28 1

Pyrazolyl alcohols, oxidation 67

Pyrones, f rom pyrazolines 213 pyrazoles from 54, 55

Reduction of the pyrazole ring

Reductive cleavage, 67-70

of pyrazolines 221 of the pyrazole ring 70-71

Rosenmund reduction 119, 122, 123, 124

Sandmeyer reaction 87, 106,324,

Semidine rearrangement 103

Skraup synthesis 104 Sommelet reaction 123 Sulfa drugs 345-50 Syndones, pyrazoles from 59-62

343

Thiocarbohydrazides, pyrazoles f rom 20-23

Thiopyrones, pyrazoles from 64 o -Toluidines, indazoles from

1, 2, 3-Tricarbonyls, pyrazoles 295-8, 299-300

from 20

Willgerodt reaction 108

888

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